612
Helvetica Chimica Acta ± Vol. 82 (1999)
AcOH/MeCN (2.75 ml), 30 min. TLC (silica gel, Polygam plates, AcOEt/(i-PrOH/NH3/H2O 7:1:2) 1:1): Rf
0.52. Bu4N ´ 3 H2O (631 mg, 2 mmol) in THF (2 ml), 4 d at r.t., final evaporation. The residue was extracted with
CHCl3 (40 ml) and H2O (40 ml), the aq. phase washed with CHCl3 (2 Â 30 ml), and the combined org. phase
evaporated. The sirupy residue was washed with MeCN (3 Â 2 ml) to give a colourless precipitate. TLC
(cellulose, i-PrOH/NH3/H2O 8 : 1 : 1): Rf 0.79. MeOH (0.5 ml), H2O (0.5 ml) and AcOH (4 ml) were added, and
the mixture was stirred at r.t. for 24 h and co-evaporated with MeOH/H2O (1 : 1, 5 Â 10 ml) and NH3/H2O (3 Â
5 ml). The residue was washed several times with EtOH and MeCN and lyophilized from H2O: 35 (17 mg).
Colourless powder. TLC (cellulose, i-PrOH/NH3/H2O 8 : 1 : 1): Rf 0.54. UV (MeOH): 259(4.55). HPLC: tR
31.52 min. FAB-MS: 1147 [M H] , 1169 [M Na] (Fig. 2).
27. Adenylyl-(2' ± 5')-adenylyl-(2' ± 5')-3'-deoxy-3'-(hexadecanoylamino)adenosine (A(2' ± 5')A(2' ± 5')Ad3'
-
(NHpalm)3'; 36). As described for 33, with 32 (70 mg, 26.4 mmol), 0.5m DBU/MeCN (5.3 ml), r.t., 24 h, 1m
AcOH/MeCN (2.65 ml), 30 min. TLC (silica gel, Polygam plates, AcOEt/(i-PrOH/NH3/H2O 7:1:2) 1:1): Rf
0.59. Bu4NF ´ 3 H2O (947 mg, 3 mmol) in THF (5 ml), 3 d at r.t., final evaporation. TLC (cellulose; i-PrOH/
NH3/H2O 8 : 1 : 1): Rf 0.77. MeOH (0.5 ml), H2O (0.5 ml), and AcOH (4 ml) were added, the mixture was
stirred at r.t. for 23 h, evaporated, co-evaporated with MeOH/H2O 1 : 1 (4 Â 15 ml), and washed several times
with EtOH. The residue was lyophilized from NH3/H2O: 36 (8.5 mg). Colourless powder. TLC (cellulose, i-
PrOH/NH3/H2O 8 : 1 : 1): Rf 0.48. HPLC: tR 32.14 min (Fig. 1). FAB-MS: 1164 [M H] , 1185 [M Na] .
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