N. Iranpoor et al. / Tetrahedron 61 (2005) 5699–5704
5703
0.6 g of Silphos; IR (KBr disk) n (cmK1): 3200, 1100, 1000,
800, 680, and 500.
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4.3. A typical procedure for the conversion of benzyl
alcohol to benzyl bromide
9. (a) Burns, A. J.; Cadogan, J. I. G. J. Chem. Soc. 1963,
5788–5796. (b) Sugimato, O.; Mori, M.; Tanji, K. Tetrahedron
Lett. 1999, 40, 7477–7478.
To a flask containing a stirring mixture of Silphos (3.0 g)
and Br2 (0.67 g, 4.2 mmol) in refluxing dry acetonitrile
(20 mL), was added benzyl alcohol (0.324 g, 3 mmol). The
orange color of the reaction mixture became yellow after
5 min and GC analysis showed the completion of the
reaction. Then, enough powdered sodium thiosulfate was
added in portions to the reaction mixture and stirred
vigorously to decolorize the unreacted bromine. The
mixture was then filtered and the solvent was evaporated
under vacuum in a rotary evaporator. Benzyl bromide was
obtained as a colorless liquid (0.265 g, 97%, bp 195 8C, lit.19
bp 196–198 8C). The product was found to be highly pure by
GC and NMR analysis. Spectral data for benzyl bromide
[100-39-0]; IR (neat) n (cmK1): 3070, 3060, 3025, 1500,
10. Anilkumar, G.; Nambu, H.; Kita, Y. Org. Proc. Res. Dev.
2002, 6, 190–191.
11. Arsted, E.; Barrett, A. G. M.; Hopkins, B. T.; Kobberling, J.
Org. Lett. 2002, 4, 1975–1977.
12. Caldarelli, M.; Habermann, J.; Ley, S. V. J. Chem. Soc., Perkin
Trans. 1 1999, 107–110.
13. Desmaris, L.; Percina, N.; Cottier, L.; Sinou, D. Tetrahedron
Lett. 2003, 44, 7589–7591.
14. Pollastri, M. P.; Sagal, J. F.; Chang, G. Tetrahedron Lett. 2001,
42, 2459–2460.
15. Iranpoor, N.; Firouzabadi, H.; Aghapour, G. Synlett 2001, 7,
1176–1178.
1
1440, 1220, 1200, 1050, 1000, 750, 690, 600, H NMR
(CDCl3) d (ppm) 7.19–7.36 (5H, m), 4.52 (2H, s); 13C NMR
(CDCl3) d (ppm) 137.4, 129.0, 128.6, 128.3, 33.5.
16. Iranpoor, N.; Firouzabadi, H.; Aghapour, G.; Vaez Zadeh,
A. R. Tetrahedron 2002, 58, 8689–8693.
17. Bandgar, B. P.; Sadavarte, V. S.; Uppalla, L. S. Tetrahedron
Lett. 2001, 951–953.
4.4. A typical procedure for the conversion of allyl
alcohol to 3-iodo-1-propene
18. Firouzabadi, H.; Iranpoor, N.; Jafarpour, M. Tetrahedron Lett.
2004, 45, 7451–7454.
19. Fluka Chemie Chemica—Biochemica 1993–1994.
20. Registry number and H NMR (CDCl3, 250 MHz) of the
products: benzyl iodide [620-05-3], d (ppm) 7.23–7.39 (5H,
m), 4.43 (2H, s); 4-methoxy-benzyl bromide [2746-25-0], d
(ppm) 6.83–7.27 (4H, m), 4.38-4.50 (2H, s), 3.79 (3H,s);
4-methoxy benzyl iodide [70887-29-5], d (ppm) 6.79–7.32
(4H, m), 4.46 (2H, s), 3.78 (3H, s); 4-chloro benzyl bromide
[622-95-7], d (ppm) 7.22–7.28 (4H, m), 4.42 (2H, s); 4-chloro-
benzyl iodide [35424-56-7], d (ppm) 7.23–7.32 (4H, m), 4.49
(2H, s); 4-nitro benzyl bromide [100-1108], d (ppm) 7.50–
8.12 (4H, m), 4.45 (2H, s); 4-nitro benzyl iodide [3145-86-6],
d (ppm) 7.50–8.23 (4H, m), 4.48 (2H, s); 1,1-diphenyl methyl
bromide [776-74-9], d (ppm) 7.44–7.50 (10H, m), 6.04 (1H,
s); 1,1-diphenyl methyl iodide [Ref. No. 17,18] d (ppm) 7.20–
7.32 (10H, m), 6.17 (1H, s); a,a0-dibromo-p-xylene [623-24-
5], d (ppm) 7.20–7.28 (4H, m), 4.43 (4H, s); a,a0-diiodo-p-
xylene, d (ppm) 7.15–7.18 (4H, m), 4.39 (4H, s); 1-bromo-2-
phenyl ethane [103-63-9], d (ppm) 7.08–7.17 (5H, m), 3.36–
3.42 (2H, m), 2.99–3.15 (2H, m); 1-iodo-2-phenyl-ethane
[17376-04-4], d (ppm) 7.00–7.12 (5H, m), 3.30–3.35 (2H, m),
2.91–2.95 (2H, d, m); 2-bromo octane [557-35-7], d (ppm)
3.82–3.91 (1H, m), 1.66–1.68 (3H, m), 1.43–1.63 (2H, m),
1.07 (2H, m), 1.28–1.30 (6H, m), 0.85–0.87 (3H, m); 2-iodo
octane [557-36-8], d (ppm) 3.85–3.92 (1H, m), 1.66–1.69 (3H,
m), 1.45–1.65 (2H, m), 1.09 (2H, m), 1.28–1.31 (6H, m), 0.87–
0.89 (3H, m); 3-bromo-1-propene [106-95-6], d (ppm) 5.96–
6.02 (1H, m), 5.26–5.31 (1H, m), 5.09-5.12 (1H, m), 3.87 (2H,
d, JZ7.2); bromo-cyclohexane [108-85-0], d (ppm) 3.32 (1H,
m), 1.38–1.72 (6H, m), 0.81–0.96 (4H, m); iodo cyclohexane
[626-62-0], d (ppm) 3.89 (1H, m), 1.40–1.75 (6H, m), 0.85-
0.99 (4H, m); adamantyl bromide d (ppm) 2.31 (6H, s), 2.08
(3H, s), 1.73 (6H, s); adamantyl iodide [768-90-1], d (ppm)
2.40 (6H, s), 2.20 (3H, s), 1.85 (6H, s); 2-bromo-2-methyl
propane [507-19-7], d (ppm) 1.76 (9H, s); 2-iodo-2-methyl
propane [558-17-8], d (ppm) 1.81 (9H, s); 9-bromomethyl
anthracene [2417-77-8], d (ppm) 8.43 (1H, s), 7.72–7.76 (4H,
To a flask containing a stirring mixture of 1 g of Silphos and
I2 (0.36 g, 1.4 mmol) in refluxing dry acetonitrile, was
added allyl alcohol (0.06 g, 1 mmol). The progress of the
reaction was monitored by GC. After the completion of the
reaction (10 min), enough powdered sodium thiosulfate was
added with vigorous stirring to react with the unreacted
iodine. The mixture was then filtered and the solvent was
removed under vacuum. Pure 3-iodo-1-propene was
obtained (0.13 g, 78%), bp 100 8C, lit.19 bp 102 8C. The
product was found to be highly pure by GC and NMR
analysis. Spectral data for 3-iodo-1-propene [556-56-9], IR
(neat) n (cmK1): 3050, 2970, 2960, 1640, 1430, 1400, 1145,
990, 910, 840, 670. 1H NMR (CDCl3) d (ppm) 6.0–6.1 (1H,
m), 5.27–5.33 (1H, m), 5.09–5.12 (1H, m), 3.89 (2H, d, JZ
7.5 Hz); 13C NMR (CDCl3) d (ppm) 135.2, 117.1, 5.3.
Acknowledgements
We gratefully acknowledge the support of this study by
Shiraz University Research Council and Management and
Programming Organization of Iran.
References and notes
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