A. A. Aly, R. M. Shaker / Tetrahedron Letters 46 (2005) 2679–2682
2681
Syst. 1999, 3, 467; (b) Hiskey, M.; Chavez, D. E.; Naud,
D. L.; Son, S. F.; Son, H. L.; Bome, C. A. Proc. Int.
Pyrotech. Semin. 2000, 27, 3.
(100.6 MHz, CDCl3) 18.80 (CH3), 31.60, 32.80, 33.60,
34.40 (CH2-CH2), 120.80 (PC-CH-5) 126.90, 130.10,
130.90, 132.00, 132.60 (PC-CH), 132.80 (PC-C), 134.00
(PC-CH), 134.80, 135.20, 135.90 (PC-C), 138.00 (PC-C-4),
166.00 (CO-amide); m/z (EI) 266 [M+1] (24), 265 [M+]
(100), 250 (40), 222 (24), 160 (40), 146 (28), 104 (65), 84
(22), 78 (18).
5. Koldobskii, G. I.; Ostrovskii, V. A. Usp. Khim. 1994, 63,
847.
6. Moderhack, D. J. Prakt. Chem./Chem.-Ztg. 1988, 340,
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7. (a) Harvill, R. K.; Herbest, R. M.; Schereiner, E. C.;
Roberts, C. W. J. Org. Chem. 1950, 15, 662; (b) Braun, J.
von; Manz, G. Ann 1931, 488, 111; (c) Vaughan, J.; Smith,
P. A. S. J. Org. Chem. 1958, 23, 1909; (d) Suzuki, H.;
Hwang, Y. S.; Nakaya, C.; Matano, Y. Synthesis 1993,
1218.
8. (a) Demko, Z. P.; Sharpless, K. B. Angew. Chem. Int. Ed.
2002, 41, 2113; (b) Demko, Z. P.; Sharpless, K. B. Angew.
Chem. Int. Ed. 2002, 41, 2110; (c) Demko, Z. P.; Sharpless,
K. B. Org. Lett. 2001, 3, 4091.
9. (a) Huisgen, R.; Sauer, J.; Sturm, H. J.; Markgraf, H.
Chem. Ber. 1960, 93, 2106; (b) Huisgen, R.; Sauer, J.;
Sturm, H. J.; Seidel, M. Chem. Ber. 1961, 94, 2503; (c)
Huisgen, R.; Seidel, M.; Wallbillich, G.; Knupfer, H.
Tetrahedron 1962, 17, 3; (d) Huisgen, R.; Grashey, R.;
Seidel, M.; Wallbillich, G.; Knupfer, H.; Schmidt, R.
Liebigs Ann. Chem. 1962, 653, 105.
10. Bryce, M. R.; Vernon, J. M. Adv. Heterocycl. Chem. 1981,
28, 183.
11. Gilchrist, T. L. The Chemistry of Functional Groups. Suppl.
C, 1983; Chapter 11.
12. Aly, A. A.; Mohamed, N. K.; Hassan, A. A.; Mourad, A.
E. Tetrahedron 1999, 55, 1111.
13. Aly, A. A.; Mourad, A. E.; El-Shaieb, K. M.; Hopf, H.
Synth. Commun. 2001, 31, 637.
19. Cram, D. J.; Dalton, C. K.; Knox, G. R. J. Am. Chem.
Soc. 1963, 85, 1088.
20. 5-Methyl-1-(40-[2.2]paracyclophanyl)-1H-tetrazole (3d):
To a solution of 1d (0.79 g, 3 mmol) in dry benzene
(200 mL) under N2 was added phosphorus(V) chloride in
portions over 20 min., (0.63 g, 3 mmol). The reaction was
followed by TLC analysis until the consumption of the
starting materials was completed and a new product of
imide chloride appeared. To the reaction mixture, a
solution of hydrazoic acid (0.15 g, 3.5 mmol)7b in dry
benzene (10 mL) was added over 10 min. The mixture was
refluxed in a water bath for 8 h. The solvent was removed
under reduced pressure and the residue was treated with
ice and water to decompose any phosphorus oxychloride
present. The organic layer was extracted with chloroform
and washed several times with water. The solvent was
removed in vacuo and the residue was treated with
absolute ethanol (150 mL) to give 3d which was collected
by filtration. Colorless crystals (Rf 0.4, CH2Cl2); yield
0.74 g (85%); mp 180 °C (acetonitrile); [Found: C, 74.60;
H, 6.20; N, 19.20%. C18H18N4 (290.37) requires C, 74.46;
H, 6.25; N, 19.29%]; mmax (KBr) 3021–2962 cmꢀ1 (Ar-CH),
2930–2852 (Aliph.-CH), 1597, 1519, 1494, 1451, 1428,
1387, 1380, 1286, 1270, 1113, 1077, 1039, 983, 959; kmax
(CH3CN, log e) 260 nm (3.40); dH (400 MHz, CDCl3) 2.38
(s, 3H, CH3), 2.50–2.56 (m, 1H, CH2–CH2), 2.80–3.25 (m,
7H, CH2–CH2), 6.55-6.68 (m, 6H, PC-H), 6.87 (dd, 1H,
PC-H, JH,H = 8.0, 1.4 Hz); dC (100.6 MHz, CDCl3) 10.80
(CH3), 32.00, 35.00, 35.40, 35.80 (CH2-CH2), 126.40,
131.80, 132.70, 133.60, 134.40, 134.90, 135.20 (PC-CH),
135.60, 136.20, 138.30, 139.10 (PC-C), 142.40 (PC-C-4),
154.40 (azomethine-C-5); m/z (EI) 290 [M+] (20), 262 (8),
221 (20), 208 (10), 158 (76), 130 (44), 105 (26), 104 (100),
84 (12), 78 (16), 56 (18).
14. Aly, A. A.; Hopf, H.; Ernst, L. Eur. J. Org. Chem. 2000,
3021.
15. Aly, A. A.; El-Shaieb, K. M. Tetrahedron 2004, 60, 3797.
16. (a) Aly, A. A. Tetrahedron 2003, 59, 6067; (b) Aly, A. A.;
Mourad, A. E.; Hassan, A. A.; Mohamed, N. K.; Ali, B.
A.; El-Sayed, M. M. Arch. Pharm. Pharm. Med. Chem.
2004, 337, 133; (c) Shaker, R. M. Phosphorus Sulfur Silicon
2003, 178, 1175; (d) Shaker, R. M. Phosphorus Sulfur
Silicon 2000, 158, 9; (e) Aly, A. A.; Shaker, R. M. J. Chem.
Res. (S) 1999, 626; (f) Aly, A. A.; Gomaa, A.-M. Can. J.
Chem. 2005, 83, 57; (g) Aly, A. A. Tetrahedron 2003, 59,
1739; (h) Aly, A. A. Org. Biomol. Chem. 2003, 1, 756; (i)
Aly, A. A. Tetrahedron Lett. 2005, 46, 443.
17. (a) Hoffmann, R. W. Dehydrobenzene and Cycloalkynes;
Academic: New York, 1968; (b) Gilchrist, T. L. In The
Chemistry of Functional Groups, Suppl. C; Patai, S.,
Rappoport, Z., Eds.; Wiley: Chichester, 1983, Chapter
11; (c) Hart, H. In The Chemistry of Triple–Bonded
Functional Groups, Suppl. C2; Patai, S., Ed.; Wiley:
Chichester, 1994, Chapter 18.
18. N-(40-[2.2]Paracyclophanyl)acetamide (1d): To a two-
necked flask (250 mL) containing a cold (0 °C) stirred
mixture of 419 (1.12 g, 5 mmol) dissolved in methanol
(150 mL) was added sodium hydroxide (0.20 g, 5 mmol)
dissolved in water (10 mL). To the reaction mixture, acetyl
chloride (0.37 g, 5 mmol) was added dropwise over
10 min. The mixture was stirred at ꢀ15 °C for 30 min.
and at rt for 1 h. The precipitate obtained was collected
by filtration and washed several times with water.
Colorless crystals (Rf 0.3, CH2Cl2); yield 1.1 g (85%); mp
146 °C (cyclohexane); [Found: C, 81.65; H, 7.20; N,
5.20%. C18H19NO (265.36) requires C, 81.47; H, 7.22; N,
5.28%]; mmax (KBr) 3220 (NH) cmꢀ1, 3060–2990 (Ar-CH),
2890–2860 (Aliph.-CH), 1682 (CO-amide); dH (400 MHz,
CDCl3) 2.20 (s, 3H, CH3), 2.30–2.70 (m, 7H, CH2–CH2),
3.20–3.35 (m, 1H, CH2–CH2), 4.10 (br, s, 1H, NH), 6.20
(d, 1 H, H-5, JH,H = 7.8 Hz), 6.40–6.74 (m, 6H, PC-H); dC
21. Reaction of 3a–d with 5; General Procedure: Benz-
enediazonium carboxylate was prepared by the same
procedure as described in reference.22 Under nitrogen
atmosphere, 5 (4 mmol) was added slowly to the stirred
and refluxed solutions of 3a–d (2 mmol) in dry acetonitrile
(250 mL) over 1 h. The reaction mixture was refluxed
until the consumption of the starting materials was
completed (reaction progress monitored by TLC analysis)
in 12–18 h. The solvent was concentrated and the residue
was filtered off. The precipitate was washed with dichlo-
romethane (200 mL). The filtrate was concentrated under
vacuum and the residue was applied to PLC on silica gel
using toluene: ethyl acetate (10:1) as eluent. The main
zones containing compounds 6a–d were extracted with
acetone and the recovered products were recrystallized
from the stated solvents.
22. Logullo, F. M. Org. Synth. Col. 1973, Vol. V, 54.
23. Colin, W. G.; Gupta, R. C.; Storr, R. J. Chem. Soc.,
Perkin Trans. 1 1984, 2827.
24. (a) Do¨pp, D.; Gomaa, M. A.-M.; Henkel, G. J. Hetero-
cyclc. Chem. 1995, 32, 603; (b) Gomaa, M. A.-M.; Do¨pp,
D. Synthesis 2003, 1545.
25. Pfau, M.; Chiriacescu, M.; Revial, G. Tetrahedron Lett.
1993, 34, 327.
26. Hopf, H.; Aly, A. A.; Swaminathan, V. N.; Ernst, L.; Dix,
I.; Jones, P. G. Eur. J. Org. Chem. 2005, 68.
27. 5-Benzyl-1-phenyl-1H-tetrazole (6a): Yellow crystals (Rf
0.5, CH2Cl2); yield 0.29 g (62%); mp 125–126 °C (ethanol)