1004
M. A. Zolfigol et al.
LETTER
Cautions: All N-nitroso amines [R1-N(NO)-R2] should be re-
garded as potentially powerful carcinogens, since most com-
pounds of these types have been shown to possess high
carcinogenic activity in experimental animals.8a
(5) Olszewska, T.; Milewska, M. J.; Gdaniec, M.; Matuszynska,
H.; Potonski, T. J. Org. Chem. 2001, 66, 501.
(6) Zolfigol, M. A.; Shirini, F.; Ghorbani Choghamarani, A.;
Taqian-nasab, A.; Keypour, H.; Salehzadeh, S. J. Chem.
Res., Synop. 2000, 420.
N-Nitrosation of N,N-Dialkyl Amines; General Procedure
A suspension of sodium nitrite, trichloroisocyanuric acid (the molar
ratio of trichloroisocyanuric acid (I) and sodium nitrite to the sub-
strate 1 was optimized: Table), amine (1, 5 mmol) and wet SiO2 (1g,
50% w/w) in dichloromethane (10 mL) were stirred vigorously at
r.t. The progress of the reaction was followed by TLC. After com-
pletion, the reaction mixture was filtered, the residue was washed
with CH2Cl2 (2 5 mL), then anhyd Na2SO4 (10 g) was added to the
filtrate and the mixture filtered after 20 min. The solvent was evap-
orated and the corresponding N-nitroso compounds (2) were ob-
tained (Table). If further purification is needed, flash
chromatography on silica gel [eluent: acetone/petroleum ether
(10:90)] provides highly pure 2.
(7) Rivera, A.; Gallo, G. I.; Joseph-Nathan, P. Synth. Commun.
1997, 27, 163.
(8) (a) Furniss B. S., Hannaford A. J., Smith P. W. G., Tatchell
A. R.; Vogels Text Book of Practical Organic Chemistry;
Longman: London and New York, 1989; 5th ed.:.
(b) Sheriner, R. L.; Reynold, T. L.; Fuson, C.; Curtin, D. Y.;
Morrill, T. C. The Systematic Identification of Organic
Compounds, 6th ed.; John Wiley and Sons: New York, 1980,
220.
(9) Castedo, L.; Riguera, R.; Vezquez, M. P. J. Chem. Soc.,
Chem. Commun. 1983, 301.
(10) Fanning, J. C.; Keefer, L. K.; Larry, K. J. Chem. Soc., Chem.
Commun. 1987, 955.
N-Nitrosation of Diethyl Amine (1b) with Trichloroisocyanuric
Acid (I), NaNO2 (II) and Wet SiO2; Typical Procedure
(11) Nakajima, M.; Warner, J. C.; Anselme, J. P. Tetrahedron
Lett. 1984, 25, 2619.
A suspension of compound 1b (0.146 g, 2 mmol), I (0.325 g, 1.4
mmol), wet SiO2 (50% w/w, 0.4 g) and II (0.289 g, 4.2 mmol) in
dichloromethane (4 mL) was stirred at r.t. for 10 min and then fil-
tered. The residue was washed with CH2Cl2 (2 5 mL). 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 0.189 g,
(93%) of pale yellow liquid (2b), bp 173–176 °C [Lit.12 mp 175–
(12) Chang, S. K.; Hrrington, G. W.; Rothstein, M.; Shergalis, W.
A.; Swern, D.; Vohra, S. K. Cancer Res. 1979, 39, 3871.
(13) Makhova, N. N.; Karpov, G. A.; Mikhailyuk, A. N.; Bova,
A. E.; Khmel´nitskii, L. I.; Novikov, S. S. Izv. Akad. Nauk
SSSR, Ser. Khim. 1978, 1, 226.
(14) Zolfigol, M. A. Synth. Commun. 1999, 29, 905; and
references cited therein.
(15) (a) Zolfigol, M. A.; Ghorbani Choghamarani, A.; Shirini, F.;
Keypour, H.; Salehzadeh, S. Synth. Commun. 2001, 31, 359.
(b) Zolfigol, M. A.; Shirini, F.; Ghorbani Choghamarani, A.;
Shiri, A.; Keypour, H.; Salehzadeh, S. Asian J. Chem. 2001,
13, 849.
1
177 °C]. H NMR (FT-NMR, 90 MHz, CDCl3-TMS): (ppm) =
3.87 (q, 2 H), 3.33 (q, 2 H), 1.16 (t, 3 H), 0.85 (t, 3 H).6
Acknowledgement
(16) Zolfigol, M. A. Tetrahedron 2001, 57, 9509; and our
references cited therein.
This research project has been supported by grant No. NRCI 32-296
of National Research Projects and with support of National Rese-
arch Council of Islamic Republic of Iran.
(17) (a) Firouzabadi, H.; Iranpoor, N.; Hazarkhani, H. Synlett
2001, 1641; and references cited therein. (b) Xiog, Z.;
Xuang, N. P.; Zhong, P. Synth. Commun. 2001, 31, 245.
(18) Singer, S. S.; Lijinsky, W.; Singer, G. M. Tetrahedron Lett.
1977, 19, 1613.
(19) Singer, S. S. J. Org. Chem. 1978, 43, 4612.
(20) Turnbull, K. J. Heterocycl. Chem. 1985, 22, 965.
(21) Richter-Addo, G. B. Acc. Chem. Res. 1999, 32, 529.
(22) Zolfigol, M. A.; Zebarjadian, M. H.; Chehardoli, G. A.;
Keypour, H.; Salehzadeh, S.; Shamsipur, M. J. Org. Chem.
2001, 66, 3619.
(23) Zolfigol, M. A.; Zebarjadian, M. H.; Sadeghi, M. M.;
Memarian, H. R.; Mohammadpoor-Baltork, I.; Shamsipur,
M. Synth. Commun. 2001, 30, 929.
(24) Zolfigol, M. A.; Zebarjadian, M. H.; Chehardoli, G.;
Mallakpour, S. E.; Shamsipur, M. Tetrahedron 2001, 57,
1627.
References
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Synlett 2002, No. 6, 1002–1004 ISSN 0936-5214 © Thieme Stuttgart · New York