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1
520
DEAN
þ
1
53.8 and 156.9 ppm; MS: (FAB, positive ion þ Na) m/e 309 [M þ H] , 331
þ
[M þ Na] .
0
0
-Amino-5 -deoxyguanosine 1
5
0
0
A stirred solution of 5 -azido-5 -deoxyguanosine 4 (3.1 g, 10 mmol) in
ꢀ
dry pyridine (50 ml) at 0 C was treated with triphenylphosphine (5.2 g,
20 mmol). After stirring at room temperature for 3 h, the resulting thick
ꢀ
suspension was re-cooled to 0 C, treated with ammonium hydroxide
solution (0.880 ammonia, 15 ml) and water (50 ml), then stirred at room
temperature for 18 h. The solvent was removed under reduced pressure,
and the residue was suspended in ethyl acetate (300 ml) and stirred at
room temperature for 15 min. The resultant solid was collected by filtration,
washed with ethyl acetate (50 ml), cold ethyl acetate/methanol (1 : 1, 50 ml)
ꢀ
0
0
and water (50 ml), then dried at 50 C under vacuum to give 5 -amino-5 -
ꢀ
1
deoxyguanosine 1 (2.2 g, 78%) as a colourless solid: m.p. 219–220 C (from
ꢀ
1
ꢀ
water) [m.p. 221 C ]; [a] À 41.6 (c 0.5, DMSO); l (MeOH): 254 nm
" 12600), 268 nm (sh) (" 9100); (0.01 N HCl); 254 nm (" 12000), 270 nm (sh)
8500); (0.01 N KOH): 264 nm (" 10600); H NMR (DMSO-d , 400 MHz):
6
D
max
(
"
1
0
0
d 2.72 (1 H, dd, J ¼ 13.6, 5.4 Hz, H-5 ), 2.79 (1 H, dd, J ¼ 13.6, 4.8 Hz, H-5 ),
0
0
0
3
.78 (1 H, m, H-4 ), 4.08 (1 H, m, H-3 ), 4.44 (1 H, m, H-2 ), 4.5–5.6 (5 H,
0
br, exchanged with D O), 5.66 (1 H, d, J ¼ 6.0 Hz, H-1 ), 6.47 (2 H,
2
1
br, exchanged with D O, NH ) and 7.93 (1 H, s, H-8) ppm; C NM R
3
2
2
(
1
DMSO-d , 100 MHz): d 43.5, 70.6, 73.2, 85.6, 86.2, 116.7, 135.7, 151.3,
6
þ
53.6 and 156.7 ppm; MS: (FAB positive ion) m/e 283 [M þ H] . Found:
C, 39.8, H, 5.3, N, 27.5%. C H N O ꢁH O requires C, 40.0, H, 5.33,
1
0
14
6
4
2
N, 28.0%.
REFERENCES
. Schattka, K.; Jastorff, B. Chem. Ber. 1972, 105, 3824–3832.
. Schattka, K.; Jastorff, B. Chem. Ber. 1974, 107, 3043–3052; Shuman,
D.A.; Bloch, A.; Robins, R.K.; Robins, M.J. J. Med. Chem. 1969, 12,
1
2
653–657; Elloumi, B.; Moreau, B.; Aguiar, L.; Jaziri, N.; Sauvage, M.;
Hulen, C.; Capman, M.L. Eur. J. Med. Chem. 1992, 27, 149–154;
Heskamp, B.M.; Veeneman, G.H.; van de Marel, G.A.; van Boeckel,
C.A.A.; van Boom, J.H. Tetrahedron. 1995, 51, 8397–8406; Li, H.;
Miller, M.J. J. Org. Chem. 1999, 64, 9289–9293.
3. Holmes, R.E.; Robins, R.K. J. Org. Chem. 1963, 28, 3483–3486.