H. Schulz et al.
48
(C55C) cm21; 1H NMR (250 MHz, [D6]-acetone): d 3.53 (s, 3H, OMe), 3.91–4.09
(m, 2H, J4 ,4a 8.8 Hz, H-40, H-4a), 4.29 (dd, 1H J4 ,4 8.8 Hz, J4 ,4a 3.4 Hz, H-400),
4.72 (d, 1H, J4a,9b 8.2 Hz, H-9b), 5.33 (s, 1H, H-6), 5.80 (s, 1H, H-2), 6.57 (s, 2H,
NH2), 7.30–7.54 (m, 5H, Ph); 13C NMR (63 MHz, [D6]-acetone): d 56.5 (OMe),
66.8 (C-4a), 69.5 (C-4), 76.0 (C-9b), 84.7 (C-7), 96.9 (C-6), 102.5 (C-2), 114.6
(CN), 120.5 (C-6a), 127.3, 128.9, 129.8, 133.7, (Ph), 138.7 (C-9a), 165.2 (C-8);
MS (CI, isobutane): m/z (%) 345 (100) [M þ H]þ.
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Anal. Calcd for C17H16N2O4 S: C, 59.29; H, 4.68; N, 8.13; S, 9.31. Found: C,
59.81; H, 4.74; N, 7.98; S, 9.07.
(2R,4aR,6S,9bR)-8-(Aminomethylenamino)-4,4a,6,9b-tetrahydro-6-met
hoxy-2-phenylthieno[20,30:4,5]pyrano[3,2-d][1,3]dioxine-7-carbonitrile
(4). A solution of 3 (300 mg, 0.87 mmol) in triethyl orthoformate (10 mL) was
heated for 2 h under reflux. Then the reaction mixture was concentrated
under reduced pressure yielding a solid, which was dissolved in a saturated
ethanolic solution of ammonia (15 mL) and stirred over night at rt. Evaporation
in vacuo supplied a light yellow solid, which after treatment with charcoal in
acetone was pure enough for the preparation of compound 5. Column chrom-
atography (toluene/acetone 2:1) furnished analytically pure 4 (305 mg, 82%)
as colorless crystals; mp 262–2658C; [a]2D2 280.58 (c 1.0, DMF); Rf 0.45
(toluene/acetone 2:1); IR (KBr): n 3400, 3143 (NH2), 2215 (CN), 1694 (C55C)
cm21 1H NMR (250 MHz, [D6]-DMSO): d 3.46 (s, 3H, OMe), 3.81–4.03
;
(m, 2H, J4 ,4a 9.6 Hz, H-40, H-4a), 4.27 (dd, 1H, J4 ,4 9.5 Hz, J4 ,4a 3.7 Hz,
H-400), 4.79 (d, 1H, J4a,9b 8.4 Hz, H-9b), 5.43 (s, 1H, H-6), 5.82 (s, 1H, H-2),
7.34–7.48 (m, 5H, Ph), 7.73 (s, 1H, NHH), 7.84 (t, 1H, CHNH2), 8.10 (d, 1H,
NHH); 13C NMR (63 MHz, [D6]-DMSO): d 56.2 (OMe), 65.7 (C-4a), 68.2 (C-4),
74.4 (C-9b), 93.4 (C-7), 95.5 (C-6), 101.1 (C-2), 114.8 (CN), 124.4 (C-6a),
126.5, 128.3, 129.3, 132.7, (Ph), 137.4 (C-9a), 155.7 (CHNH2), 168.2 (C-8); MS
(70 eV): m/z (%) 371 (100) [M]þ.
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Anal. Calcd for C18H17N3O4 S: C, 58.21; H, 4.61; N, 11.31; S, 8.63. Found: C,
58.00; H, 4.69; N, 11.07; S, 8.35.
(2R,4aR,6S,11bR)-4,4a,6,11b-Tetrahydro-6-methoxy-2-phenyl-[1,3]diox-
ino[400,500:50,60]pyrano[30,40:4,5]thieno[2,3-d]pyrimidin-7-amine (5).
A
solution of 4 (300 mg, 0.81 mmol) in anhydrous DMF (10 mL) was treated
under stirring with NaH (35 mg, 0.9 mmol, 60%) for 1 h at room temperature.
After addition of ice water the mixture was extracted with dichloromethane
(3 ꢀ 30 mL). The combined organic layers were washed with water
(2 ꢀ 30 mL), dried (Na2SO4), and evaporated. Purification by column chrom-
atography (toluene/acetone 2:1) and recrystallization from methanol yielded
5 (264 mg, 71%) as colorless needles; mp 259–2628C; [a]2D2 þ1828 (c 1.0,
DMF); Rf 0.35 (toluene-acetone 2:1); IR (KBr): n 3486, 3284 (NH2), 1637
(C55C) cm21
;
1H NMR (250 MHz, [D6]-DMSO): d 3.57 (s, 3H, OMe),
3.91–4.09 (m, 2H, J4 ,4a 10.4 Hz, H-40, H-4a), 4.40 (dd, 1H, J4 ,4 9.2 Hz, J4 ,4a
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