Investigation of Acid-Catalyzed Hydrolysis of 4-Nitrophenyl-N-Acetyl-4-Methylbenzenesulfonimidate in Dioxane-Water Solutions

Yıl 2023, , 526 - 537, 30.09.2023

Seyhan Öztürk , Halil Kütük

https://doi.org/10.31202/ecjse.1269612

Öz

The hydrolysis of 4-nitrophenyl N-acetyl-4-methylbenzenesulfonimidate in aqueous 20%, 40%, and 60% (v/v) dioxane solutions of mineral acids was investigated. Rate maxima are observed for both perchloric and sulfuric acids since hydrolysis was studied over a wider range of acidity in 20%, and 40% (v/v) dioxane. Similarly, rate maxima are observed perchloric and hydrochloric acid in 60% (v/v) dioxane at high acid concentration. Analyses of the data by the Cox–Yates excess acidity method and temperature effects indicate hydrolysis by an A-2 mechanism.

Anahtar Kelimeler

Sulfonimidate, Acid-catalyzed, Hydrolysis, A-2 mechanism, Excess Acidity

Kaynakça

• [1]. A. Tota, M. Andresini, M. Colella, R. S. Dibenedetto, L. Degennaro, and R. Luisi, “(1R,2S,5R)-2-Isopropyl-5-methylcyclohexyl (R)-4-methylbenzenesulfonimidate,” Molbank, vol. 2022, no. 4, Dec. 2022, doi: 10.3390/M1518.
• [2]. P. M. Matos and R. A. Stockman, “Synthetic approaches and applications of sulfonimidates,” Organic and Biomolecular Chemistry, vol. 18, no. 33. Royal Society of Chemistry, pp. 6429-6442, Sep. 07, 2020. doi: 10.1039/d0ob01191f.
• [3]. E. S. Levchenko, L. N. Markoviski, and A. v. Kirsanov, “N-Alkylarenesulfonimidoyl Chlorides and Aryl N-Alkylarenesulfonimid,” Journal of Organic Chemistry of the USSR, vol. 3, p. 1273, 1967.
• [4]. A. K. Roy, G. T. Burns, G. C. Lie, and S. Grigoras, “Poly(alkyl/aryloxothiazenes): inorganic polymers with a sulfur(VI)-nitrogen backbone. Synthesis, characterization, and theoretical calculations,” J Am Chem Soc, vol. 115, no. 7, pp. 2604-2612, Apr. 1993, doi: 10.1021/ja00060a009.
• [5]. D. Leca, L. Fensterbank, emmanuel Lacote, and M. Malacria, “A New and Practical One-Pot Access to Sulfonimidates,” American Chemical Society, Org. Lett., vol. 4, no. 23, pp. 4093-4095, 2002.
• [6]. Y. Liang and W. Lipscom, “Substrate and inhibitor binding to human carbonic anhydrase II: a theoretical study. In: Botre ́ F, ed. Inhibitors in the carbonic anhydrase from biochemistry and physiology and clinical medicine,” Weinheim: VCH Publishers, pp. 50-64, 1991.
• [7]. T. H. Lowry and K. S. Richardson, Mechanism and Theory in Organic Chemistry , 3rd ed. New York: Harper & Row Publishers, 1987.
• [8]. B. García, F. J. Hoyuelos, S. Ibeas, and J. M. Leal, “Hydrolysis Mechanisms for Indomethacin and Acemethacin in Perchloric Acid,” J Org Chem, vol. 71, no. 10, pp. 3718-3726, May 2006, doi: 10.1021/jo052561k.
• [9]. H. Kutuk and J. Tillett, “Kinetics and Mechanisms of The Acid-Catalysed Hydrolyses of 4-Nitrophenyl-N-Aroyl-Areneiminosulphonates,” Phosphorus Sulfur Silicon Relat Elem, vol. 85, no. 1–4, pp. 217-224, Dec. 1993, doi: 10.1080/10426509308038201.
• [10]. H. Kutuk, Y. Bekdemir, and N. Turkoz, “The Synthesis and Substituent Effect of the Acid Catalyzed Hydrolysis of Amidosulfites,” Phosphorus Sulfur Silicon Relat Elem, vol. 181, no. 4, pp. 931-937, Apr. 2006, doi: 10.1080/10426500500272186.
• [11]. H. Kutuk and H. Yakan, “The Mechanisms of Acid-Catalyzed Hydrolysis of N-(4-Substituted Arylthio) Phthalimides,” Phosphorus Sulfur Silicon Relat Elem, vol. 186, no. 7, pp. 1460-1469, Jul. 2011, doi: 10.1080/10426507.2010.517584.
• [12]. S. Ozturk, S. Shahabi, and H. Kutuk, “Kinetics and Mechanisms of Acid-Catalyzed Hydrolysis of Some N-(4-Substitutedaryl) Succinimide Compounds,” Journal of the chemical society of pakistan, vol. 44, no. 2, pp. 186-186, 2022, doi: 10.52568/000998/JCSP/44.02.2022.
• [13]. E. S. Levchenko, I. N. Berzino, and A. v Kirsanov, “Chlorides and Aryl Esters of N- Aroylareneiminosulfonic Acids,” Journal of Organic Chemistry of the USSR, p. 1251, 1965.
• [14]. K. T. Douglas, J. P. Hallett, F. M. Said, and J. G. Tillett, “Acid-Catalysed Hydrolysis and Alcoholysis of 4-Nitrophenyl-N-Acetyl-Phenyliminosulphonate,” Phosphorous and Sulfur and the Related Elements, vol. 37, no. 1–2, pp. 21-26, May 1988, doi: 10.1080/03086648808074348.
• [15]. J. T. Edward and S. C. R. Meacock, “Hydrolysis of amides and related compounds. Part I. Some benzamides in strong aqueous acid,” Journal of the Chemical Society (Resumed), p. 2000, 1957, doi: 10.1039/jr9570002000.
• [16]. I. Kapovits, F. Ruff, and Á. Kucsman, “Acid-catalysed hydrolysis of S(IV)N bond in N-sulphonyl sulphilimines—I,” Tetrahedron, vol. 28, no. 16, pp. 4405–4412, Jan. 1972, doi: 10.1016/S0040-4020(01)88963-8.
• [17]. R. A. Cox and K. Yates, “Kinetic equations for reactions in concentrated aqueous acids based on the concept of ‘excess acidity,’” Can J Chem, vol. 57, no. 22, pp. 2944-2951, Nov. 1979, doi: 10.1139/v79-479.
• [18]. R. A. Cox and K. Yates, “Excess acidities. A generalized method for the determination of basicities in aqueous acid mixtures,” J Am Chem Soc, vol. 100, no. 12, pp. 3861-3867, Jun. 1978, doi: 10.1021/ja00480a033.