1624
M. A. Zolfigol, A. Bamoniri
LETTER
General Procedure for N-Nitrosation of Secondary Amines
A suspension of sodium nitrite, silica sulfuric acid (the molar ratio
of silica sulfuric acid (I) and sodium nitrite to the substrate 1
was optimized, Table 2), amine (1, 5 mmol) and wet SiO2 (1 g, 50%
w/w) in dichloromethane (10 mL) were stirred vigorously magneti-
cally at r.t. The progress of the reaction was followed by TLC. The
reaction mixture was filtered after completion of the reaction. The
residue was washed with CH2Cl2 (2 5 mL). Then anhyd Na2SO4
(10 g) was added to the filtrate when was filtered after 20 min. The
solvent was evaporated and the N-nitroso compounds (2) were ob-
tained (Table 2). If further purification was needed, flash chroma-
tography on silica gel [eluent: acetone–petroleum ether bp 60–80 °C
(10:90)] provide highly pure 2.
(6) Zolfigol, M. A.; Shirini, F.; Ghorbani-Choghamarani, A.;
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Tatchell, A. R. Vogels Text Book of Practical Organic
Chemistry, 5th ed.; Longman: London/New York, 1989.
(b) Sheriner, R. L.; Reynold, T. L.; Fuson, C.; Curtin, D. Y.;
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220–223.
(9) Castedo, L.; Riguera, R.; Vezquez, M. P. J. Chem. Soc.,
Chem. Commun. 1983, 301.
N-Nitrosation of Diphenyl Amine (1j) with Silica Sulfuric Acid
(I), NaNO2 (II) and Wet SiO2; Typical Procedure
(10) Fanning, J. C.; Keefer, L. K.; Larry, K. J. Chem. Soc., Chem.
Commun. 1987, 955.
A suspension of compound 1j (0.338 g, 2 mmol), I (0.4 g 2 mmol),
wet SiO2 (50% w/w, 0.4 g) and II (0.207 g, 3 mmol) in dichloro-
methane (4 mL) was stirred at r.t. for 20 min (the progress of the
reaction was monitored by TLC) and then filtered. Anhyd Na2SO4
(5 g) was added to the filtrate. After 15 min the resulting mixture
was also filtered. Dichloromethane was removed by water bath
(35–40 °C) and simple distillation. The yield was 0.361 g, (99%) of
crystalline yellow solid (2j), mp 63–66 °C [Lit.8 mp 67 °C].
(11) Nakajima, M.; Warner, J. C.; Anselme, J. P. Tetrahedron
Lett. 1984, 25, 2619.
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SSSR, Ser. Khim. 1978, 1, 226.
(14) Zolfigol, M. A. Synth. Commun. 1999, 29, 905.
(15) Zolfigol, M. A.; Ghorbani-Choghamarani, A.; Hazarkhani,
H. Synlett 2002, 1002.
(16) (a) Zolfigol, M. A. Tetrahedron 2001, 57, 9509; and
references cited therein. (b) Zolfigol, M. A.; Torabi, M.;
Mallakpour, S. E. Tetrahedron 2001, 57, 8381. (c) Shirin,
F.; Zolfigol, M. A.; Mallakpour, B.; Mallakpour, S. E.;
Hagipour, A. Tetrahedron Lett. 2002, 43, 1555.
(17) Riego, J. M.; Sedin, Z.; Zaldivar, J. M.; Marziano, N. C.;
Tortato, C. Tetrahedron Lett. 1996, 37, 513.
(18) Turro, N. J. Tetrahedron 1987, 43, 1589.
(19) Olah, G. A.; Molhotra, R.; Narang, S. C. J. Org. Chem. 1978,
43, 4628.
Acknowledgement
This research project has been supported by grant No. NRCI 32-296
of National Research Projects and with support of National
Research Council of Islamic Republic of Iran.
References
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Synlett 2002, No. 10, 1621–1624 ISSN 0936-5214 © Thieme Stuttgart · New York