Synthesis of (E)-9-(Propen-1-yl)-9H-adenine
339
by HPLC. Water (500 mL) was added and the suspension containing the precipitated solid
was maintained at 20–25◦C for 1 h. The product was collected and washed with 250 mL of
chilled water to yield (133.0 g, 95%) of a colorless solid, mp. 177–180◦C.
1H NMR (300 MHz, DMSO-d6): δ 1.36 (d, 3H), 2.94 (s, 3H), 4.41 (m, 2H), 5.2
(m, 1H), 7.3 (brs, 2H), 8.12 (s, 1H), 8.0 (s, 1H); 13C NMR (70 MHz, DMSO-d6) : δ 156.0
(C-6), 152.6 (C-2), 149.8 (C-4), 141.2 (C-8), 118.5 (C-5), 47.0 (C-1ꢀ), 76.8 (C-2ꢀ), 18.4
(C-3ꢀ), 37.5 (C-mesylate methyl); MS : m/z 271.8 (M + + 1).
Anal. Calcd for C9 H13 N5 O3 S : C, 39.84; H, 4.83. Found: C, 39.75; H, 4.95
Preparation of (E)-9-(Prop-1-enyl)-9H-adenine (2)
1-(Adenin-9-yl)propan-2-yl methanesulfonate (4) (20.0 g, 0.073 mol) and potassium tert-
butoxide (8.5 g, 0.075 mol) were mixed with DMF (150 mL) at 25–30◦C. The reaction
mass was stirred at 25–30◦C for 3 h, completion of reaction was monitored by HPLC, the
reaction mixture was poured slowly into water (1500 mL) and the suspension obtained
was stirred at 25–30◦C for 1 h. The product mixture was extracted into chloroform (3 ×
100 mL), washed with water and concentrated to afford a mixture of 1 and 2 as a thick
solid residue (9.50 g, 95%). It was dissolved in water (25 mL) at 70–75◦C and stirred for
30 min. The clear solution was cooled slowly to 0–5◦C and stirred for 1 h and the resulting
solid was collected, washed with chilled water (10 mL), dried under vacuum to afford pure
2 (8.50 g, 85%) as a white solid, mp. 203–205◦C, lit.7 mp. 197◦C. IR (cm−1): 3370, 3312,
1
3140, 1645, 1590; H NMR (300 MHz, DMSO-d6): δ 1.78 (dd, 3H), 6.55 (m, 1H), 7.1
(dd, 1H), 7.35 (brs, 2H), 8.36 (s, 1H), 8.42 (s, 1H); 13C NMR (70 MHz, DMSO-d6) : δ
156.0 (C-6), 152.9 (C-2), 148.4 (C-4), 138.5 (C-8),
121.6 (C-1ꢀ), 118.9 (C-5), 115.9 (C-2ꢀ), 15.06 (C-3ꢀ); MS : m/z 176.26 (M + + 1).
The combined mother liquors (35 mL) from the isolation of 2 was distilled under
vacuum (660 mm Hg) to give a crude solid which was purified by crystallization from
acetonitrile to yield (0.50 g, 5%) of 1 as a pale yellow solid, mp. 143–145◦C, lit.8 mp.
1
143–145◦C. H NMR (300 MHz, DMSO-d6) : δ 4.83 (dd, 2H), 5.18 (bd, 1H), 5.33 (bd,
1H), 6.05 (m, 1H), 6.2 (bs, 2H), 7.82 (s, 1H), 8.38 (s, 1H)
Acknowledgment
The authors are thankful to Tyche Industries Limited for financial assistance.
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