Role of water in determining organic reactivity in aqueous binary solvents

• Authors: Siim Salmar , Jaak Järv , Tiina Tenno , Ants Tuulmets
• Languages of publication: EN

Abstracts

EN

Kinetic data for organic reactions in various binary water-organic solvent mixtures were collected and quantitatively analysed in terms of linear-free-energy relationships by using tert-butyl chloride (2-chloro-2-methylpropane) solvolysis as the reference system. Linear similarity plots for these kinetic data were determined for solvent systems ranging from pure water mixtures up to considerable amount of cosolvent, and 161 similarity coefficients were calculated from slopes of these plots. The existence of these linear plots demonstrated that the solvent effects are of some common nature in all analysed reaction mixtures independent of the reaction type and the cosolvent used. Therefore it was concluded that the observed effects could be connected to the specific solvating properties of water, which govern reactivity even in significant dilution of water by an organic cosolvent. This conclusion was supported by the linear interrelationship between the slopes of similarity plots of different reactions, and hydrophobicity parameters log P of the reacting compounds. The relative solvent effects observed in binary water-organic solvent mixtures were for the first time directly related to the structure of reacting compounds. [...]

Keywords

EN

Solvent effects; LFE relationships; Organic-aqueous solutions; Similarity coefficients; Hydrophobic interactions

• Publisher: De Gruyter Open
• Journal: Open Chemistry
• Year: 2012
• Volume: 10
• Issue: 5
• Pages: 1600-1608

Dates

published

1 - 10 - 2012

online

21 - 7 - 2012

Contributors

author

Siim Salmar

• Institute of Chemistry, University of Tartu, 50411, Tartu, Estonia

author

Jaak Järv

• Institute of Chemistry, University of Tartu, 50411, Tartu, Estonia

author

Tiina Tenno

• Institute of Chemistry, University of Tartu, 50411, Tartu, Estonia

author

Ants Tuulmets

• Institute of Chemistry, University of Tartu, 50411, Tartu, Estonia

References

• [1] R. Breslow, In: M. Lindström (Ed.), Organic Reactions in Water (Blackwell Publishers, Oxford, 2007) Chapter 1
• [2] T.J. Mason, P. Cintas, In: J. Clark, D. Macquarrie (Eds), Handbook of Green Chemistry (Blackwell Publishers, Oxford, 2000)
• [3] F. Franks (Ed.), Water: a Comprehensive Treatise (Plenum Press, New York, 1972–1982) Vols. 1–7
• [4] C. Reichardt, T. Welyon, Solvents and Solvent Effects in Organic Chemistry, 4th edition (Wiley-VCH, Weinheim, 2011)
• [5] J.B.F.N. Engberts, In: F. Franks (Ed.) Water: a Comprehensive Treatise (Plenum Press, New York, 1979) Vol. 6, Chapter 4
• [6] M.J. Blandamer, J. Burgess, J.B.F.N. Engberts, P. Warrick Jn., J. Mol. Liq. 52, 15 (1992) http://dx.doi.org/10.1016/0167-7322(92)80094-X[Crossref]
• [7] D.N. Shin, J.W. Wijnen, J.B.F.N. Engberts, A. Wakisaka, J. Phys. Chem. B 106, 6014 (2002) http://dx.doi.org/10.1021/jp020414+[Crossref]
• [8] O.A. El Seoud, Pure Appl. Chem. 81, 697, (2009) http://dx.doi.org/10.1351/PAC-CON-08-09-27[Crossref]
• [9] P.L. Silva, M.A.S. Trassi, C.T. Martins, O.A. El Seoud, J. Phys. Chem. B 113, 9512 (2009) http://dx.doi.org/10.1021/jp902272g[Crossref]
• [10] W. Blokzijl, J.B.F.N. Engberts, Angew. Chem. 105, 1610 (1993) http://dx.doi.org/10.1002/ange.1761051104[Crossref]
• [11] W. Blokzijl, J.B.F.N. Engberts, Angew. Chem. Int. Ed. Engl. 32, 1545 (1993) http://dx.doi.org/10.1002/anie.199315451[Crossref]
• [12] S. Otto, J.B.F.N. Engberts, Org. Biomol. Chem. 1, 2809 (2003) http://dx.doi.org/10.1039/b305672d[Crossref]
• [13] C. Tanford, The Hydrophobic Effect, 2nd edition (Wiley, New York, 1980)
• [14] N.T. Southall, K.A. Dill, A.D.J. Haymet, J. Phys. Chem. B 106, 521 (2002) http://dx.doi.org/10.1021/jp015514e[Crossref]
• [15] U.M. Lindström, Chem. Rev. 102, 2751 (2002) http://dx.doi.org/10.1021/cr010122p[Crossref]
• [16] C. Li, Chem. Rev. 105, 3095 (2005) http://dx.doi.org/10.1021/cr030009u[Crossref]
• [17] C.T. Martins, M.S. Lima, O.A. El Seoud, J. Org. Chem. 71, 9068 (2006) http://dx.doi.org/10.1021/jo061533e[Crossref]
• [18] K.A. Connors, In: G. Wypych (Ed.), Handbook of Solvents (ChemTec Publishing, Toronto, 2001) 281
• [19] W. Blokzijl, J.B.F.N. Engberts, J. Jager, M.J. Blandamer, J. Phys. Chem. 91, 6022 (1987) http://dx.doi.org/10.1021/j100307a041[Crossref]
• [20] T. Rispens, C. Caballeiro-Lago, J.B.F.N. Engberts, Org. Biomol. Chem. 3, 597 (2005) http://dx.doi.org/10.1039/b414593c[Crossref]
• [21] T. Rispens, J.B.F.N. Engberts, J. Phys. Org. Chem. 18, 725 (2005) http://dx.doi.org/10.1002/poc.926[Crossref]
• [22] T.W. Bentley, H.C. Harris, Z.H. Ryu, G.T. Lim, D.D. Sung, S.R. Szajda, J. Org. Chem. 70, 8963 (2005) http://dx.doi.org/10.1021/jo0514366[Crossref]
• [23] T.W. Bentley, M.S. Garley, J. Phys. Org. Chem. 19, 341 (2006) http://dx.doi.org/10.1002/poc.1084[Crossref]
• [24] M.J. D’Souza, M.J. McAneny, D.N. Kevill, J.B. Kyong, S.H. Choi, Beilstein J. Org. Chem. 7, 543 (2011), and references therein. http://dx.doi.org/10.3762/bjoc.7.62[Crossref]
• [25] D.N. Kevill, K.H. Park, H.J. Koh, J. Phys. Org. Chem. 24, 378 (2011) http://dx.doi.org/10.1002/poc.1767[Crossref]
• [26] K.H. Park, D.N. Kevill, J. Phys. Org. Chem. 25, 267 (2011) http://dx.doi.org/10.1002/poc.1906[Crossref]
• [27] R. Breslow, J. Phys. Org. Chem. 19, 813 (2006) http://dx.doi.org/10.1002/poc.1037[Crossref]
• [28] A. Tuulmets, S. Salmar, H. Hagu, J. Phys. Chem. B 107, 12891 (2003) http://dx.doi.org/10.1021/jp035714l[Crossref]
• [29] A. Tuulmets, H. Hagu, S. Salmar, G. Cravotto, J. Järv, J. Phys. Chem. B 111, 3133 (2007) http://dx.doi.org/10.1021/jp0682199[Crossref]
• [30] A. Tuulmets, J. Järv, S. Salmar, G. Cravotto, J. Phys. Org. Chem. 21, 1002 (2008) http://dx.doi.org/10.1002/poc.1415[Crossref]
• [31] A. Tuulmets, S. Salmar, J. Järv, Sonochemistry in Water Organic Solutions (Nova Science Publishers, New York, 2010)
• [32] A. Tuulmets, J. Järv, T. Tenno, S. Salmar, J. Mol. Liq. 148, 94 (2009) http://dx.doi.org/10.1016/j.molliq.2009.06.008[Crossref]
• [33] A. Williams, Free Energy Relationships in Organic and Bio-organic Chemistry, (RSC, Cambridge, 2003)
• [34] E. Grunwald, S. Winstein, J. Am. Chem. Soc. 70, 846 (1948) http://dx.doi.org/10.1021/ja01182a117[Crossref]
• [35] R.I. Zalewski, T.M. Krygowski, J. Shorter, Similarity Models in Organic Chemistry, Biochemistry and Related Fields (Elsevier, New York, 1991)
• [36] A.H. Fainberg, S. Winstein, J. Am. Chem. Soc. 78, 2770 (1956) http://dx.doi.org/10.1021/ja01593a033[Crossref]
• [37] R.E. Robertson, Can. J. Chem. 50, 1353 (1972) http://dx.doi.org/10.1139/v72-212[Crossref]
• [38] K. Heinonen, E. Tommila, Suomen Kem. B38, 9 (1965)
• [39] S. Winstein, E. Grunwald, H.W. Jones, J. Am. Chem. Soc. 73, 2700 (1951) http://dx.doi.org/10.1021/ja01150a078[Crossref]
• [40] D.N. Kevill, M.J. D’souza, J. Chem. Res. 61–66 (2008)
• [41] E. Tommila, A. Koivisto, J.P. Lyyra, K. Antell, S. Heimo, Ann Acad. Sci. Fennicae A11, Nr. 47 (1952)
• [42] A.H. Fainberg, S. Winstein, J. Am. Chem. Soc. 79, 1602 (1957) http://dx.doi.org/10.1021/ja01564a022[Crossref]
• [43] D.N. Kevill, M.J. D’souza, J. Org. Chem. 69, 7044 (2004) http://dx.doi.org/10.1021/jo0492259[Crossref]
• [44] M. Harati, M.R. Gholami, Int. J. Chem. Kinetics 37(2), 90 (2005) http://dx.doi.org/10.1002/kin.20041[Crossref]
• [45] A.A. Sosunov, A.P. Kilimov, V.V. Smirnov, Zh. Obch. Khimii 40, 2688 (1970) (in Russian)
• [46] Y. Marcus, Solvent Mixtures-Properties and Selective Solvation (M. Dekker, New York, Basel, 2002)
• [47] K. Egashira, N. Nishi, J. Phys. Chem. B 102, 4054 (1998) http://dx.doi.org/10.1021/jp9806359[Crossref]
• [48] T. Takamuku, T. Yamaguchi, M. Asato, M. Matsumoto, N. Nishi, Z. Naturforsch., Part A 55a, 513 (2000)
• [49] A. Wakasaka, S. Komatsu, Y. Usui, J. Mol. Liq. 90, 175 (2001) http://dx.doi.org/10.1016/S0167-7322(01)00120-9[Crossref]
• [50] S. Dixit, J. Crain, W.C.K. Poon, J.L. Finney, A.K. Soper, Nature 416, 829 (2002) http://dx.doi.org/10.1038/416829a[Crossref]
• [51] Y. Liu, X. Luo, Z. Shen, J. Lu, X. Ni, Optical Rev. 13, 303 (2006) http://dx.doi.org/10.1007/s10043-006-0303-3[Crossref]
• [52] A. Wakisaka, K. Matsura, J. Mol. Liq. 129, 25 (2006) http://dx.doi.org/10.1016/j.molliq.2006.08.010[Crossref]
• [53] N.P. Hu, D. Wu, K. Cross, S. Burikov, T. Dolenko, S. Patsaeva, D.W. Schaefer, J. Agric. Food Chem. 57, 7394 (2010) http://dx.doi.org/10.1021/jf100609c[Crossref]
• [54] A.H. Fainberg, S. Winstein, J. Am. Chem. Soc. 79, 1602 (1957) http://dx.doi.org/10.1021/ja01564a022[Crossref]
• [55] A.H. Fainberg, S. Winstein, J. Am. Chem. Soc. 79, 1608 (1957) http://dx.doi.org/10.1021/ja01564a023[Crossref]
• [56] T.W. Bentley, I.S. Koo, S.J. Norman, J. Org. Chem. 56, 1604 (1991) http://dx.doi.org/10.1021/jo00004a048[Crossref]
• [57] T.W. Bentley, I.S. Koo, H. Choi, G. Llewellyn, J. Phys. Org. Chem. 21, 251 (2008) http://dx.doi.org/10.1002/poc.1308[Crossref]
• [58] A. Leo, C. Hansch, D. Elkins, Chem. Rev. 71, 525 (1971) http://dx.doi.org/10.1021/cr60274a001[Crossref]
• [59] C. Hansch, Acc. Chem. Res. 2, 232 (1969) http://dx.doi.org/10.1021/ar50020a002[Crossref]
• [60] ACD/ChemSketch Freeware (Advanced Chemistry Development, Inc., Canada, 2010)
• [61] M.H. Abraham, J.C. Dearden, G.M. Bresnen, J. Phys. Org. Chem. 19, 242 (2006) http://dx.doi.org/10.1002/poc.1027[Crossref]
• [62] P. Sikk, A. Aaviksaar, A. Abduvahhabov, Eesti NSV Tead. Akad. Toim., Keem., Geol. 26(3), 242 (1977) (in Russian)
• [63] K.A. Connors, M.J. Mulski, A. Paulson, J. Org. Chem. 57, 1794 (1992) http://dx.doi.org/10.1021/jo00032a036[Crossref]
• [64] J.M. LePree, M.J. Mulski, K.A. Connors, J. Chem. Soc. Perkin Trans. 2 1491 (1994) [Crossref]
• [65] N.J. Buurma, L. Pastorello, M.J. Blandamer, J.B.F.N. Engberts, J. Am. Chem. Soc. 123, 11848 (2001) http://dx.doi.org/10.1021/ja010617w[Crossref]

Identifiers

DOI

10.2478/s11532-012-0080-8