Summary.
The stoichiometric protonation constants (log β) of some disubstituted aniline derivatives in ethanol–water mixtures (0–90% ethanol by volume) at 25.0 ± 0.1°C were firstly submitted to factor analysis in order to obtain the number factors which affect the variation of the whole data sets and, afterwards, submitted to target factor analysis to identify these factors. The influence of solvatochromic parameters in the interactions between aniline derivatives and the solvent studied was identified and quantified. The general equation of Kamlet and Taft was reduced for these mixtures to two terms using combined factor analysis (FA) and target factor analysis (TFA): the independent term and the hydrogen-bond donating ability, α (HBD), solvatochromic parameters. Further, the quasi-lattice quasi-chemical (QLQC) theory of preferential solvation has been applied to quantify the preferential solvation by water of electrolytes in ethanol–water mixtures. The effects of the substituents on the protonation constants, the additivities of these effects, and the applicability of the Hammett equation to the behavior of substituents are also discussed. Further, Hammett’s reaction constant for the protonation of disubstituted anilines has been obtained for all the solvent mixtures and correlates well with α (HBD) of the solvent.
Similar content being viewed by others
References
J Barbosa R Berges I Toro V Sanz-Nebot (1997) Talanta 44 1271 Occurrence Handle10.1016/S0039-9140(96)02188-1 Occurrence Handle1:CAS:528:DyaK2sXktVWhu74%3D
H Sigel RB Martin R Tribolet HK Häring R Malini-Balakrishnan (1985) Eur J Biochem 152 187 Occurrence Handle1:CAS:528:DyaL2MXmtV2rsbc%3D
R Kauski CY Murray (1993) Tetrahedron Lett 34 2263
YK Li A Kuliopulos AS Mildrais P Talalay (1993) Biochemistry 32 1816 Occurrence Handle1:CAS:528:DyaK3sXhtF2ksrk%3D
JM Clifford WF Smyth (1974) Analyst 99 241 Occurrence Handle10.1039/an9749900241 Occurrence Handle1:CAS:528:DyaE2MXh
H Kelly A Huggett S Dawling (1982) Clin Chem 28 1478 Occurrence Handle1:CAS:528:DyaL38XkvVCmuro%3D
I Shehatta (2002) Helv Chim Acta 85 2125 Occurrence Handle10.1002/1522-2675(200207)85:7<2125::AID-HLCA2125>3.0.CO;2-U Occurrence Handle1:CAS:528:DC%2BD38Xmt1Oqtrw%3D
Reichardt C (1990) Solvents and Solvent Effects in Organic Chemistry. 2nd edn. VCH, Weinheim
Y Altun (2004) Solution Chem 33 479 Occurrence Handle1:CAS:528:DC%2BD2cXms1Cgurs%3D Occurrence Handle10.1023/B:JOSL.0000037772.55748.a3
J Barbosa G Fonrodona I Marqués V Sanz-Nebot I Toro (1997) Anal Chim Acta 351 397 Occurrence Handle10.1016/S0003-2670(97)00234-1 Occurrence Handle1:CAS:528:DyaK2sXmtFKiu7Y%3D
J Barbosa G Fonrodona I Marqués S Butí I Toro (1997) Trends Anal Chem 16 104 Occurrence Handle1:CAS:528:DyaK2sXhvVGksLw%3D
B Hemmateenejad H Sharghi M Akhond M Shamsipur (2003) J Solution Chem 32 215 Occurrence Handle10.1023/A:1022982200712 Occurrence Handle1:CAS:528:DC%2BD3sXisVGgsr4%3D
J Lior (1999) J Solution Chem 28 1
E Casassas G Fonrodona A De Juan R Tauler (1991) Chemom Intell Lab Syst 12 29 Occurrence Handle10.1016/0169-7439(91)80106-Z Occurrence Handle1:CAS:528:DyaK38XmvVKnsg%3D%3D
J Barbosa I Marqués G Fonrodona D Barrón V Sanz-Nebot (1997) Trends Anal Chem 16 140 Occurrence Handle1:CAS:528:DyaK2sXjtVOjsLk%3D
MJ Kamlet RW Taft (1976) J Am Chem Soc 98 377 Occurrence Handle10.1021/ja00418a009 Occurrence Handle1:CAS:528:DyaE28XovFeqtA%3D%3D
MJ Kamlet JL Abboud RW Taft (1976) J Am Chem Soc 99 6027
MJ Kamlet JL Abboud MH Abraham RW Taft (1983) J Org Chem 48 2877 Occurrence Handle10.1021/jo00165a018 Occurrence Handle1:CAS:528:DyaL3sXkvVOgsbc%3D
K Dimroth CA Reichardt (1966) Anal Chem 215 344 Occurrence Handle1:CAS:528:DyaF28XovVaruw%3D%3D
I Marqués G Fonrodona S Buti J Barbosa (1999) Trends Anal Chem 18 472
A Gustavo González D González-Arjona (1995) Anal Chim Acta 312 295
K Hagemark (1968) J Phys Chem 72 2316 Occurrence Handle10.1021/j100853a006 Occurrence Handle1:CAS:528:DyaF1cXksVKmsbc%3D
Y Marcus (1988) J Chem Soc Faraday Trans I 84 1465 Occurrence Handle1:CAS:528:DyaL1cXhslCmtLc%3D
AK Mandal SC Lahiri (1978) J Indian Chem Soc 55 495 Occurrence Handle1:CAS:528:DyaE1cXls1aru78%3D
Perrin DD, Armarego WLF (1992) Purification of Laboratory Chemicals. Pergamon
Serjeant EP (1984) Potentiometry and Potentiometric Titrations, Chapt 5, Electrodes for Potentiometry. Wiley, New York Chichester Brisbane Toronto Singapore
JH Park MD Jang DS Kim PW Carr (1990) J Chrom 513 107 Occurrence Handle10.1016/S0021-9673(01)89429-2 Occurrence Handle1:CAS:528:DyaK3cXltl2gsLc%3D
Marcus Y (2002) Solvent Mixtures Properties and Selective Solvation Dekker, New York Basel
C Hansch A Leo RW Taft (1991) Chem Rev 91 165 Occurrence Handle10.1021/cr00002a004 Occurrence Handle1:CAS:528:DyaK3MXhs1ehsLo%3D
Martell AE, Motekaitis RJ (1988) The Determination and Use of Stability Constants. VCH, Weinheim
Malinowski ER (2002) Factor Analysis in Chemistry, 3rd ed. Wiley, New York
D Gonzáles-Arjona J Antonio Mejías A Gustavo González (1994) Anal Chim Acta 295 119
D Gonzáles-Arjona J Antonio Mejías A Gustavo González (1994) Anal Chim Acta 297 473
MATLAB, The Math Works, Inc., Natick, MA
C Golumbic G Goldbach (1951) J Amer Chem Soc 73 3966 Occurrence Handle10.1021/ja01152a121 Occurrence Handle1:CAS:528:DyaG38Xit1GjsQ%3D%3D
Smith JW (1968) In: Patai S (ed) The Chemistry of Amino Group, chapt 4. Wiley, London
C Bernasconi W Koch H Zollinger (1963) Helv Chim Acta 46 1184 Occurrence Handle10.1002/hlca.19630460414 Occurrence Handle1:CAS:528:DyaF3sXksVGht7s%3D
KC Gross PG Seybold (2001) J Org Chem 66 6919 Occurrence Handle10.1021/jo010234g Occurrence Handle1:CAS:528:DC%2BD3MXmvVKit74%3D
Perrin DD (1965) Dissociation Constants of Organic Bases in Aqueous Solution. Butterworths, London
Albert A, Serjant EP (1962) Ionization Constants of Acids and Bases. Methuen, London
AD Courville (1966) Compt Rend C 262 1196
NI Kudryashova NV Khromov-Borisov (1966) Zh Org Khim 2 578 Occurrence Handle1:CAS:528:DyaF28XksVOjsL4%3D
AL De AK Atta (1985) Can J Chem 63 2245
RG Bates (1971) J Electroanal Chem 29 6 Occurrence Handle10.1016/0368-1874(71)85121-3
AL De (1984) Electrochimia Acta 29 683 Occurrence Handle1:CAS:528:DyaL2cXltlSjsLg%3D
AL De AK Atta (1987) J Chem Eng Data 32 117 Occurrence Handle10.1021/je00047a033 Occurrence Handle1:CAS:528:DyaL2sXjvFegtQ%3D%3D
AS Quist WL Marshall (1968) J Phys Chem 72 684 Occurrence Handle1:CAS:528:DyaF1cXmtlaktg%3D%3D
AS Quist WL Marshall (1968) J Phys Chem 72 1536 Occurrence Handle1:CAS:528:DyaF1cXktVGksrk%3D
Kamlet MJ, Gal JF, Maria PC, Taft RW (1985) J Chem Soc Perkin Trans 2, 1583
Y Marcus (2001) Monatsh Chem 132 1387 Occurrence Handle1:CAS:528:DC%2BD3MXptVamu74%3D
YG Wu M Tabata T Takamuku (2002) J Solution Chem 31 381 Occurrence Handle10.1023/A:1015859315320 Occurrence Handle1:CAS:528:DC%2BD38Xksl2lur4%3D
Y Marcus Y Migron (1991) J Phys Chem 95 400 Occurrence Handle1:CAS:528:DyaK3MXltVKjsA%3D%3D
C Kalidas G Hefter Y Marcus (2000) Chem Rev 100 819 Occurrence Handle10.1021/cr980144k Occurrence Handle1:CAS:528:DC%2BD3cXht1aitb4%3D
Clarke K, Rothwell K (1960) J Chem Soc 1885
RJL Andon JD Cox EFG Herington (1954) Trans Faraday Soc 50 918 Occurrence Handle10.1039/tf9545000918 Occurrence Handle1:CAS:528:DyaG2MXit1KjsQ%3D%3D
Johnson CD (1973) The Hammett Equation. Cambridge University Press, London
Perrin DD, Demosey B, Serjeant EP (1981) pKa Prediction for Organic Acid and Bases. Chapman & Hall, London
J Lior (1999) J Solution Chem 28 1
Author information
Authors and Affiliations
Corresponding author
Rights and permissions
About this article
Cite this article
Altun, Y. Study of Solvent Effects on the Protonation of Functional Group of Disubstituted Anilines: Factor Analysis Applied to the Correlation between Protonation Constants and Solvatochromic Parameters in Ethanol–Water Mixtures. Monatsh. Chem. 136, 1993–2006 (2005). https://doi.org/10.1007/s00706-005-0371-2
Received:
Accepted:
Published:
Issue Date:
DOI: https://doi.org/10.1007/s00706-005-0371-2