N-(2,6-Dinitro-4-trifluoromethylphenyl)aniline derivatives were prepared by anilino-dechlorination of 4-chloro-3, 5-dinitrobenzotrifluoride. IR, UV and 1H NMR studies suggested an intramolecular hydrogen bond between the amino hydrogen and one o-nitro group. An addition-elimination mechanism was suggested based on the second-order kinetics and the dependence of rates on the nature and the position of the substituent in the aniline ring, as well as the high negative values of ρ(-3.14, −3.16, −3.01). Such values indicate a positive charge on the aniline nitrogen in the transition state and that the rate is affected by the polar effect of the substituent. The β value (0.85 at 30°C) indicates an appreciable degree of bond formation in the transition state.
EggimanW., SchmidP., and ZollingerH., Helv. Chim. Acta., 1975, 58, 257.
6.
BanjokoO., and RahmanK.U., J. Chem. Soc., Perkin Trans. 2, 1981, 11.
7.
BuncelE., CramptonM.R., StraussM.J., and TerrierF.Electron Deficient Aromatic and Anionic Sigma Complexes, Elsevier, Amsterdam, 1984.
8.
TerrierF., Nucleophilic Aromatic Displacement. The Influence of the Nitro Group, Ed. FeuerH., VCH, New York, 1991.
9.
NudelmanN.S., The Chemistry of Amino, Nitroso, Nitro and Related Groups, 1996, Ch. 26, Ed. PataiS., J. Wiley & Sons, London.
10.
NudelmanN.S., SaviniM., SilvanaC.E., NicotraV., and YankelevichJ., J. Chem. Soc., Perkin Trans. 2, 1999, 1627.
11.
IsanborC., EmokpaeT.A., and CramptonM.R., J. Chem. Soc., Perkin Trans. 2, 2002, 2019.
12.
HaratiM., and GholamiM.R., Int. J. Chem. Kinet., 2005, 37, 90.
13.
AsgharB.H.M., and CramptonM.R., Org. Biomol. Chem., 2005, 3, 3971.
14.
RyanJ.J., and HumffrayA.A., J. Chem. Soc., B, 1967, 1300.
15.
SpinelliD., ConsiglioG., NotoR., and FrennaV., J. Org. Chem., 1976, 41, 968
16.
El-HegazyF.M., Z-Abdel-FattahS., HamedE.A., and SharafS.M., J. Phys. Org. Chem., 2000, 13, 549
17.
El-BardanA.A., El-SubruitiG.M., El-HegazyF.M., and HamedE.A., Int. J. Chem. Kinet, 2002, 34, 645.
18.
OkamatoT., and BrownH.C., J. Org. Chem., 1957, 22, 485.
19.
RobertsJ.D., VaughanC.W., CarlsmithL.A., and SemenovL., J. Am. Chem. Soc., 1956, 78, 611; 1956, 79, 601
20.
HamedE.A., Int. J. Chem. Kinet, 1997, 29, 599 and references cited therein.
21.
HamedE.A., El-BardanA.A., SaadE.F., GoherG.A., and HassanG.M., J. Chem. Soc., Perkin Trans. 2, 1997, 2415
22.
El-BardanA.A., J. Phys. Org. Chem., 1999, 12, 347.
23.
HamedE.A., Int. J. Chem. Kinet., 1997, 29(5), 515.
24.
El-MallahN.M., HamedE.A., and El-BardanA.A., Egypt. J. Chem., 1995, 38, 319.
25.
(a) FathallaM.F., IbrahimM.F., and HamedE.A., J. Chem. Res., 2004, 150; (b) M.F. Fathalla, Int. J. Chem Kinet, 2006, 38, 159.
26.
FathallaM.F., and HamedE.A., J. Chem. Res., 2006, 413.
27.
BellamyL.J., The Infrared Spectra of Complex Molecules, Wiley, New York, 1978.
28.
SocratesG., Infrared Characteristic Group Frequencies, Wiley & Sons, 1980.
29.
SilversteinR.M., BasslerG.C., and MorrillT.C., Spectrometric Identification of Organic Compound, 4th edn, Wiley, New York, 1991.
30.
(a) KamletM.J., AdolphH.G., and HoffsommerJ.C., J. Am. Chem. Soc., 1964, 86, 4108; (b). M.J. Kamlet, R.R. Misesiger, J.C. Hoffsommer, J.C. Dacons and H.G. Adolph, J. Chem. Soc. B, 1968, 1147.
31.
(a) AlvaroC.E.S., and NudelmanN.S., Arkivoc, 2003, 95; (b) N.S. Nudelman, C.E.S. Alvaro and J.S. Yankelevich, J. Chem. Soc., Perkin Trans. 2, 1997 and references therein, (c) G.N. Orusha and I. Onyido, J. Chem. Soc., Perkin Trans. 2, 1988, 971; (d) N.S. Nudelman, M. Marder and A. Gurevich, J. Chem. Soc., Perkin Trans. 2, 1993, 229. (e) N.S. Nudelman and D.R. Palleros, J. Org. Chem., 1983, 48, 1613.
32.
(a) CramptonM.R., EmokpaeT.A., HowardJ.A.K., IsanborC., and MondalR., Org Biomol Chem., 2003, 1, 1004; (b) M.R. Crampton, B. Gibson, J. Chem., Soc., Perkin Trans. 2, 1981, 533. (c) M.R. Crampton, C.J. Greenhalgh, J. Chem. Soc., Perkin Trans. 2, 1983. 1175; (d) Y.J. Hasegawa, J. Chem. Soc., Perkin Trans. 2, 1985. 87; (e) M.R. Crampton and P. Routlede, J. Chem. Soc., Perkin Trans. 2, 1984, 573; (f) R.A. Chamberlin and M.R. Crampton, J. Chem. Soc., Perkin Trans. 2, 1994. 425.
33.
CramptonM.R., and WillisonW.J., J. Chem. Soc., Perkin Trans. 2, 1974, 238 and references therein.
34.
BevanC.W.L., and HirstJ., J. Chem. Soc, 1956, 254.
35.
VinsonK.L., and DanmernbergJ.J., J. Am. Chem. Soc., 1989, 111, 2777.
36.
ButcherR.J., GilardiR., Flippen-AndersonJ.L., and GeorgeC.New J. Chem, 1992, 16, 679.
37.
(a). WolfJ.J., ZietschA., OeserT., and BolocanI., J. Org. Chem., 1998, 63, 5164; (b). F. Gerard, A. Hardy and A. Becuwe, Acta. Crystallogr. Sect. 1993, 49, 1215.
38.
ChapmanN.B., ChaudhuryD.K., and ShorterJ., J. Chem. Soc., 1975, 1962.
39.
WepsterB.M., El-VerkedP., and Van BekkumH., Rec. Trav. Chim., 1959, 78, 815.
40.
ForlaniL., Gazz. Chim. Ital., 1982. 205, 112.
41.
JonkiW.T., and RathinmmalN., J. Ind. Chem. Soc., 1987, 64, 250.
42.
PatelR.D., Int. J. Chem, Kinet., 1992, 24, 541.
43.
BiggiG., and PietraF., J. Chem. Soc. B, 1971, 44
44.
HirstJ., and RahmanK.U., J. Chem. Soc. Perkin Trans. 2, 1973, 2119.
45.
BevanC.W.L., HirstJ., and UwamuW.O., Nigerian J. Chem. Soc., 1962, 1875.
46.
BordwellF.G., and HughesD.L., J. Am. Chem. Soc., 1986, 108, 5991.
47.
GandlerJ.R., SetiarahardjoI.U., TufonC., and ChenC., J. Org. Chem., 1992, 57, 4169.
48.
DixonJ.E., and BruiceT.C., J. Am. Chem. Soc., 1972, 94, 2052.
49.
BrenelliE.C.S., MoranP.J.S., and RodrigueJ.A.R., J. Chem. Res. (S)., 1989, 12, 389
50.
BrenelliE.C.S., MoranP.J.S., J. Chem. Soc. Perkin Trans. 2, 1989, 1219.
51.
DarioL., AngelamariaM., DanielaS., VladislavV., and IrinaO., New J. Chem., 1998, 22(1), 71.
52.
LewisE.S., Investigation of Rates and Mechanisms, 3rd Ed., Wiley, New York, 1974.
