Full-text resources of PSJD and other databases are now available in the new Library of Science.
Visit https://bibliotekanauki.pl

PL EN


Preferences help
enabled [disable] Abstract
Number of results

Journal

2006 | 4 | 1 | 56-67

Article title

Protonation acidity constants for benzotoluidides in sulfuric acid solutions

Content

Title variants

Languages of publication

EN

Abstracts

EN
The protonation of o-, m-and p-benzotoluidide in sulfuric acid solutions is studied by UV spectroscopy in the 190–350 nm region. Principal component analysis is applied to estimate the contributions of the effect of protonation and the medium effect. For the substances studied in this work, the first principal component (PC) captures about 98 % of the variance and the second PC ∼100 % of the cumulative percentage variance in the 210–350 nm region. The same spectral region is used for calculation of the ionization ratio from the coefficients of the first PC and mole fractions of the base and its conjugate acid. Using these data and Hammett's equation (pK
BH
+ = H
X + log I), the pK
BH
+ values for the protonation reaction are obtained. The dissociation constants as well as the solvent parameters m* (∼0.43) and ϕ (∼0.60) are calculated using the Excess Acidity Method (-pK
BH
+= 2.28–2.30) and the Bunnett-Olsen Method (-pK
BH
+= 2.24–2.28). The probable sites of protonation are discussed.

Publisher

Journal

Year

Volume

4

Issue

1

Pages

56-67

Physical description

Dates

published
1 - 3 - 2006
online
1 - 3 - 2006

Contributors

  • Institute of Chemistry, Faculty of Natural Sciences and Mathematics, Sts. Cyril & Methodius University, 1001, Skopje, Republic of Macedonia
  • Institute of Chemistry, Faculty of Natural Sciences and Mathematics, Sts. Cyril & Methodius University, 1001, Skopje, Republic of Macedonia

References

  • [1] J.T. Edward and S.C. Wong: “Ionization of Carbonyl Compouns in Sulfuric Acid. Correction for Medium Effects by Characteristic Vector Analysis”, J. Am. Chem. Soc., Vol. 99, (1977), pp. 4229–4232. http://dx.doi.org/10.1021/ja00455a003[Crossref]
  • [2] R.A. Cox and K. Yates: “Medium effects in protonation equilibrium studies. Accurate acidity constants using the excess acidity method”, Can. J. Chem., Vol. 59, (1981), pp. 1560–1567. http://dx.doi.org/10.1139/v81-230[Crossref]
  • [3] R.A. Cox, L.M. Druet, A.E. Klausner, T.A. Modro, P. Wan and K. Yates: “Protonation acidity constants for some benzamides, acetamides, and lactams”, Can. J. Chem., Vol. 59, (1981), pp. 1568–1573. http://dx.doi.org/10.1139/v81-231[Crossref]
  • [4] G. Stojković and B. Andonovski: “UV Study of the Protonation of Benzamide and N-phenylbenzamide in Sulfuric Acid Media”, In: Proceedings, 3rd Aegan Analytical Chemistry Days, Polihnitos, Lesvos, Greece, University of Athens, Athens, (2002), pp. 498–501.
  • [5] E.R. Malinowski and D.G. Howery: Factor Analysis in Chemistry, Wiley, New York, 1980.
  • [6] Ü. Haldna: “Estimation of the Basicity Constants of Weak Bases by the Target Testing Method of Factor Analysis”, Prog. Phys. Org. Chem., Vol. 18, (1990), pp. 65–75.
  • [7] Ü. Haldna and A. Murshak: “Estimation of the Basicity Constants of Weak Bases by the Target Testing Method of Factor Analysis”, Comput. Chem., Vol. 8, (1988), pp. 201–204. http://dx.doi.org/10.1016/0097-8485(84)80006-6[Crossref]
  • [8] J.L. Simonds: “Application of characteristic vector analysis to photographic and optical response data”, J. Opt. Soc. Am., Vol. 53, (1963), pp. 968–974. http://dx.doi.org/10.1364/JOSA.53.000968[Crossref]
  • [9] R.L. Reeves: “The protonation and indicator behavior of some ionic azobenzenes in aqueous sulfuric acid”, J. Am. Chem. Soc., Vol. 88, (1966), pp. 2240–2247. http://dx.doi.org/10.1021/ja00962a029[Crossref]
  • [10] R.I. Zalewski: “Adaptation of Characteristic Vector Analysis and Titration Curve Analysis for calculations of p K BH + from Ultraviolet-Visible Spectral Data”, J. Chem. Soc. Perkin Trans. II, (1979), pp. 1637-1639. [Crossref]
  • [11] L. Jovevska, F. Anastasova and V. Aleksić: “The synthesis of some N-[4-substituted phenyl]-3-acetoxybenzthioamides and their N1,N3-disubstituted amidrazones”, Synth. Commun., Vol. 26, (1996), pp. 279–286.
  • [12] E.F. van Zyl: “A survey of reported synthesis of methaqualone and some positional and structural isomers”, Forensic Sci. Int., Vol. 122, (2001), pp. 142–149. http://dx.doi.org/10.1016/S0379-0738(01)00484-4[Crossref]
  • [13] N.G. Kundu and G. Chaudhuri: “Copper-catalysed heteroannulation with alkynes: a general and highly regio-and stereoselective method for the synthesis of (E)-2-(2-arylvinyl) quinazolinones”, Tetrahedron, Vol. 57, (2001), pp. 6833–6842. http://dx.doi.org/10.1016/S0040-4020(01)00637-8[Crossref]
  • [14] X. Zhang, C.J. Wang, L.H. Liu and Y.B. Jiang: “Reversal of the intramolecular charge transfer in p-dimethylaminobenzanilides by amido aniline substitution”, J. Phys. Chem. B, Vol. 106, (2002), pp. 12432–12440. http://dx.doi.org/10.1021/jp026369n[Crossref]
  • [15] X. Zhang, C.H. Liu, L.H. Liu, F.Y. Wu, L. Guo, X.Y. Sun, C.J. Wang, Y.B. Jiang: “Intramolecular charge transfer with N-benzoylaminonaphthalenes. 1-aminonaphthalene versus 2-aminonaphthalene as electron donors”, Org. Biomol. Chem., Vol. 1, (2003), pp. 728–732. http://dx.doi.org/10.1039/b210106h
  • [16] A.D. Taneja, N.U.M. Rao, H.P. Tiwari and C.S.G. Prasad: “Effect of temperature on the ionization constants of some β-diketones”, J. Inorg. Nucl. Chem., Vol. 36, (1974), pp. 2039–2042. http://dx.doi.org/10.1016/0022-1902(74)80719-0[Crossref]
  • [17] I. Kuzmanovski: “Chemometrics and more”, In: Proceedings, XVIII Congress of Chemists and Technologists of Macedonia, Ohrid, Macedonia, The Society of Chemists and Technologists of Macedonia, Skopje, (2004), pp. 209.
  • [18] H.H. Jafé and M. Orchin: Theory and Applications of Ultraviolet Spectroscopy, John Wiley and Sons, Inc., New York, 1965.
  • [19] F.T. Luo, Y.T. Tao, S.L. Ko, C.H. Chuen and H. Chen: “Efficient electroluminescent material for light-emitting diodes from 1,4-distyrylbenzene derivatives”, J. Mater. Chem., Vol. 12, (2002), pp. 47–52. http://dx.doi.org/10.1039/b109392d[Crossref]
  • [20] R.A. Cox and K. Yates: “Acidity function: an update”, Can. J. Chem., Vol. 61, (1983), pp. 2225–2243. http://dx.doi.org/10.1139/v83-388[Crossref]
  • [21] 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, (1978), pp. 3861–3867. http://dx.doi.org/10.1021/ja00480a033[Crossref]
  • [22] A. Bagno and G. Scorrano: “Acid-base properties of organic solvents”, J. Am. Chem. Soc., Vol. 110, (1988), pp. 4577–4582. http://dx.doi.org/10.1021/ja00222a014[Crossref]
  • [23] R.I. Zalewski and G.E. Dunn: “Protonation of conjugated ccarbonyl groups in sulfuric acid solutions. II. Protonation and basicity of αsβ-unsaturated alicyclic ketones”, Can. J. Chem., Vol. 47, (1969), pp. 2263–2270. http://dx.doi.org/10.1139/v69-366[Crossref]
  • [24] B.S. Andonovski and G.M. Stojkovic: “UV study of indole and 3-acetylindole in phosphoric and hydrochloric acid solutions”, Acta Chim. Slov., Vol. 47, (2000), pp. 349–362.

Document Type

Publication order reference

Identifiers

YADDA identifier

bwmeta1.element.-psjd-doi-10_1007_s11532-005-0004-y
JavaScript is turned off in your web browser. Turn it on to take full advantage of this site, then refresh the page.