# QSPR study on pK_{a} values of N-methoxy-polynitroaniline derivatives

Article

Received:

Accepted:

- 52 Downloads

## Abstract

A QSPR study is presented for acidities of thirteen N-methoxy-polynitroaniline derivatives. Hammett σ values are known for *meta* and *para* substituents, and in the present study values are introduced for *ortho*-substituents in these N-methoxy-polynitroaniline derivatives. Hammett σ values for *ortho*-substituents in these N-methoxy-polynitroaniline derivatives were obtained by multiplying *para* values with 0.65.

### Keywords

*N-methoxy-polynitroanilines*

*acidity*

*QSPR*

*Hammett σ constants*

## Preview

Unable to display preview. Download preview PDF.

### References

- [1]G.W. Wheland:
*Resonance in Organic Chemistry*, Wiley, New York, 1955.Google Scholar - [2]I.D. Rae: “A proton magnetic resonance study of molecular overcrowding in N-alkyl-
*o*—nitroanilines”,*Austral. J. Chem.*, Vol. 18, (1965), pp. 1807–1810.CrossRefGoogle Scholar - [3]E. Kolehmainen, K. Laihia, G. Stanciuc and A.T. Balaban: “Strong
*para*-substituent effects on rotational barriers in N-alkoxy-4-R-2,6-dinitrobenzenamines. Dynamic^{1}H-NMR study”,*Rev. Roum. Chim.*, Vol. 44, (1999), pp. 475–478.Google Scholar - [4]G. Stanciuc, M.T. Caproiu, A. Caragheorgheopol, H. Caldararu, A.T. Balaban and R.I. Walter: “Factors affecting stability and equilibria of free radicals. XII. N-Alkoxypicrylamines and ESR spectra of the corresponding capto-dative persistent aminyls”,
*J. Magn. Reson.*, Vol. 75, (1987), pp. 63–72.Google Scholar - [5]G. Stanciuc, M.T. Caproiu, A. Caragheorgheopol, H. Caldararu, T. Constantinescu and A.T. Balaban: “Factors affecting stability and equilibria of free radicals. XVI. Preparation and EPR spectra of capto-dative N-alkoxy-dinitrophenyl-aminyls”,
*Rev. Roum. Chim.*, Vol. 34, (1989), pp. 1895–1905.Google Scholar - [6]G. Stanciuc, M.T. Caproiu, A. caragheorgheopol, H. Caldararu, T. Constantinescu and A.T. Balaban: “Factors affecting stability and equilibria of free radicals. XV. EPR evidence of formation of N-alkoxypicramides on oxidation of N-alkoxy-dinitroanilines. Electronic structure of aminyl radicals”,
*Z. Naturforsch.*, Vol. 44b, (1989), pp. 1459–1463.Google Scholar - [7]N. Zarna, G. Stanciuc, T. Constantinescu, F. Chiraleu, H. Caldararu, A. Caragheorgheopol, M.T. Caproiu, M. Ionecu and A.T. Balaban: “Electronic structure and acido-basic properties of some N-alkoxy-polynitroanilines”,
*Roum. Chem. Quart. Rev.*, Vol. 2, (1994), pp. 67–81.Google Scholar - [8]T.J. Sumi, G. Stanciuc, S. Kasa and H. Joela: “Hyperfine coupling of N-alkoxy-N-polynitrophenylaminyl radicals determined by ENDOR and TRIPLE resonance spectroscopy”,
*Magn. Reson. Chem.*, Vol. 33, (1995), pp. 511–517.CrossRefGoogle Scholar - [9]N. Zarna, T. Constantinescu, G. Stanciuc, A. Caragheorgheopol, H. Caldararu, A.T. Balaban, K. Laihla and E. Kolehmainen: “Hydrophobic supramolecular complexes of various cations with 18-crown-6 as the ligand and
*N*-methoxy-pinramide as the anion pair in a water/methylene chloride two-phase system: complexes with isn't in document-amino acids, their characteristics and conditions for formation”,*Supramolecular Science*, Vol. 2, (1995), pp. 37–40.CrossRefGoogle Scholar - [10]G. Stanciuc, N. Zarna, N. Spataru, T. Constantinescu, A. Caragheorgheopol, H. Caldararu and A.T. Balaban: “Factors affecting stability and equilibria of free radicals. Part XXII. Bond dissociation energy of N-alkoxypolynitroanilines”,
*Rev. Roum. Chim.*, Vol. 41, (1996), pp. 755–761.Google Scholar - [11]I.C. Covaci, T. Constantinescu, M.T. Caproiu, C. Draghici, P. Ionita, C. Luca, G. Stanciuc, M. Maganu and A.T. Balaban: “3,5-Dinitro-4-methoxyaminobenzioc acid and its derivatives”,
*Rev. Roum. Chim.*, Vol. 44, (1999), pp. 333–340.Google Scholar - [12]D.O. Popescu, Ionita, N. Zarna, I. Covaci, A. Stoica, A. Zarna, D. Nourescu, F. Spafiu, M.T. Caproiu, C. Luca, F. Badea, T. Constantinescu and A.T. Balaban: “Hydrazyl and aminyl analogs, liquid membranes and stationary phases for gas chromatography”,
*Roum. Chem. Quart. Rev.*, Vol. 6, (1998), pp. 271–282.Google Scholar - [13]I.C. Covaci, T. Constantinescu, M.T. Caproiu, F. Dumitrascu, C. Luca and A.T. Balaban: “New N-methoxy-dinitro-aniline derivatives: Synthesis, structure and pK
_{α}values”,*Rev. Roum. Chim.*, Vol. 44, (1999), pp. 531–537.Google Scholar - [14]I.C. Covaci, T. Constantinescu, M.T. Caproiu, C. Luca and A.T. Balaban: “Solid supramolecular complexes of potassium salts of N-methoxynitroaniline derivatives and Methoxyamino-3,5-dimitropyridine with 18-crown-6 ether”,
*Eur. J. Org. Chem.*, (2000), pp. 3569–3573.Google Scholar - [15]N. Zarna, G. Stanciuc, T. Constantinescu, A.T. Balaban, K. Laihla and E. Kolehmainen: “Hydrophobic supramolecular complexes of alkali cations with 18-crown-6 as ligand and N-methoxy-2,4,6-trinitroaniline as pair anion in a two-phase system”,
*Rev. Roum. Chim.*, Vol. 41, (1996), pp. 875–881.Google Scholar - [16]A.T. Balaban, N. Frangopol, N. Negoita, P.T. Frangopol and M. Paraschiv: “Factors affecting stability and equilibria of free radicals. V. Synthesis and spectra of polynitrophenyl-alkoxy-amines”,
*Rev. Roum. Chim.*, Vol. 14, (1969), pp. 941–945.Google Scholar - [17]T. Constantinescu, M.T. Caproiu, N. Zarna, H. Caldararu, G. Stanciuc, M. Radu, V. Badescu and A.T. Balaban: “Reaction of 2,2-diphenyl-1-picrylhydrazyl (DPPH) with N-alkoxy di-and trinitroanilines”,
*New J. Chem.*, Vol. 41, (1997), pp. 575–579.Google Scholar - [18]H.H. Jaffé: “A reexamination of the Hammett equation”,
*Chem. Rev.*, Vol. 53, (1953), pp. 191–261.CrossRefGoogle Scholar - [19]P.R. Wells: “Linear free energy relationships”,
*Chem. Rev.*, Vol. 62, (1962), pp. 171–219.Google Scholar - [20]L.P. Hammett: “The effect of structure on the reaction of organic compounds. Benzene derivatives”,
*J. Am. Chem. Soc.*, Vol. 59, (1937), pp. 96–103.CrossRefGoogle Scholar - [21]K.B. Wiberg: “Substituent Effects on the Acidity of Weak Acids. 2. Calculated Gas-Phase Acidities of Substituted Benzoic Acids”,
*J. Org. Chem.*, Vol. 67, (2002), pp. 4787–4794.CrossRefGoogle Scholar - [22]K.B. Wiberg: “Substituent Effects on the Acidity of Weak Acids. 1. Bicyclo(2.2.2.)octane-1-carboxylic Acids and Bicyclo(1.1.1)pentane-1-carboxylic Acids”,
*J. Org. Chem.*, Vol. 67, (2002), pp. 1613–1617.CrossRefGoogle Scholar - [23]C. Hansch and A. Leo:
*Substituent Constants for Correlation Analysis in Chemistry and Biology*, Wiley-Interscience, New York, 1979.Google Scholar - [24]C. Hansch, A. Leo and R.W. Taft: “A Survey of Hammett Substituent Constants and Resonance and Field Parameters”,
*Chem. Rev.*, Vol. 91, (1991) pp. 165–195.CrossRefGoogle Scholar - [25]A. Pross, L. Radom and R.W. Taft: “Theoretical approach to substituent effects. phenols and phenoxide ions”,
*J. Org. Chem.*, Vol. 45, (1980), pp. 818–826.CrossRefGoogle Scholar - [26]R.D. Topsom: “Discussion of theory and experiment”,
*Prog. Phys. Org. Chem.*, Vol. 16, (1987), pp. 85–124.Google Scholar - [27]M. Charton: “The application of the Hammett equation to ortho-substituted benzene reaction series”,
*Can. J. Chem.*, Vol. 38, (1960), pp. 2493–2499.CrossRefGoogle Scholar - [28]V. Balish and M. Uma: “Steric enhancement of resonance”,
*Tetrahedron Lett.*, Vol. 25, (1960), pp. 21–25.CrossRefGoogle Scholar - [29]M.J. Kamlet: “Spectral effects of hydrogen-bonding in substituted anilines”,
*Israel J. Chem.*, Vol. 1, (1963), pp. 428–429.Google Scholar

## Copyright information

© Central European Science Journals 2005