Reaktion #6364

Reaktionsgleichung

(R)-9-[2-(diethoxyphosphorylmethoxy)-3-hydroxypropoxy)adenine

trimethylsilyl bromide

→

(R)-9-[3-Hydroxy-2-(phosphonomethoxy)propoxy]adenine

Lösungsmittel

DMF

Reaktionsbedingungen

Aufarbeitung

1. 1
   SonstigeThe solvent was removed
2. 2
   SonstigeThe solid residue was crystallised from acetone/water (0.1 g, 77%), m.p. 200°-205°
3. 3
   Sonstige[α]D25 (0.1M NaOH)-11.5° (c=0.2)

Vorschrift

To a solution of (R)-9-[2-(diethoxyphosphorylmethoxy)-3-hydroxypropoxy)adenine (0.16 g, 0.43 mmol) in dry DMF (3 ml) was added trimethylsilyl bromide (0.56 ml, 4.3 mmol) and the solution stirred at ambient temperature for 4 hours. The solvent was removed under reduced presence and the residue co-evaporated with acetone/water 1:1 (x3). The solid residue was crystallised from acetone/water (0.1 g, 77%), m.p. 200°-205°. UV: λmax (EtOH), 260 (11,800) nm. IR: νmax (KBr) 3449, 3400, 3199, 3105, 2951, 2897, 1711, 1680, 1612, 1569, 1467, 1420, 1355, 1330, 1305, 1244, 1216, 1128, 1080, 924, 866 cm-1. 1H NMR: δH [(CD3)2SO]3.54 (2H, m, CH2OH), 3.70-3.85 (3H, m, OCH2P, CH), 4.36 (1H, dd, J=11 Hz, J=7 Hz, NOCHB), 4.55 (1H, dd, J=11 Hz, J=3 Hz, NOCHA), 7.51 (2H, br.s, D2O exchangeable NH2), 8.17 (1H, s, H-2 or H-8), 8.50 (1H, s, H-2 or H-8), 3.5-7.0 (3H, broad, PO(OH)2, OH). Found: C, 32.07; H, 4.73; N, 20.46%. C9H14N5O5P 1 H2O requires: C, 32.05; H, 4.78; N, 20.76%. m/z: (FAB, thioglycerol matrix) 320 (MH+). [α]D25 (0.1M NaOH)-11.5° (c=0.2).

Quelle