1056
Hasník, Pohl, Klepetářová, Hocek:
J = 5.6, OH); 5.00 (t, 1 H, JOH,5′ = 5.6, OH-5′); 5.36 (d, 1 H, JOH,3′ = 4.2, OH-3′); 6.46 (t, 1 H,
J1′,2′ = 7.4, 6.3, H-1′); 8.72 (s, 1 H, H-8); 8.82 (s, 1 H, H-2). 13C NMR (100.6 MHz, DMSO-d6):
36.41 (CH2-pur); 39.09 (CH2-2′); 59.32 (CH2OH); 61.52 (CH2-5′); 70.61 (CH-3′); 83.61
(CH-1′); 87.89 (CH-4′); 133.02 (C-5); 143.91 (CH-8); 149.87 (C-4); 151.53 (CH-2); 159.52
20
(C-6). IR (KBr): 3401, 2928, 1601, 1400, 1335, 1213, 1055. [α]D –15.8 (c 2.72, H2O). For
C
12H14N4O4·1/2H2O (289.2) calculated: C 49.82%, H 5.92%, N 19.37%; foun d: C 50.12%,
H 5.76%, N 19.14%.
6-[(Methylcarbamoyl)methyl]-9-(β-D-ribofuranosyl)-9H-purine (7h ). Prepared from purin e 7d
(500 m g, 0.75 m m ol) an d Et3N·3HF (612 µl, 3.75 m m ol) in THF (2.5 m l). Product was
lyoph ilized to give 213 m g (88%) of 7h as a wh ite solid. MS (FAB): 324 (10, M + 1), 192 (100),
161 (60), 135 (55). HRMS (FAB): for C13H18N5O5 calculated 324.1308, foun d 324.1316.
1H NMR (499.8 MHz, DMSO-d6): 2.60 (d, 3 H, J = 4.7, CH3N); 3.57 (ddd, 1 H, Jgem = 12.0,
J5′b,OH = 6.1, J5′b,4′ = 4.1, H-5′b); 3.69 (ddd, 1 H, Jgem = 12.0, J5′a,OH = 5.2, J5′a,4′ = 4.1, H-5′a);
3.96 (s, 2 H, CH2-pur); 3.98 (td, 1 H, J4′,5′ = 4.1, J4′,3′ = 3.6, H-4′); 4.19 (td, 1 H, J3′,OH = J3′,2′
=
4.9, J3′,4′ = 3.6, H-3′); 4.65 (ddd, 1 H, J2′,OH = 6.1, J2′,1′ = 5.8, J2′,3′ = 4.9, H-2′); 5.13 (dd, 1 H,
JOH,5′ = 6.1, 5.2, OH-5′); 5.25 (d, 1 H, JOH,3′ = 4.9, OH-3′); 5.56 (d, 1 H, JOH,2′ = 6.1, OH-2′);
6.03 (d, 1 H, J1′,2′ = 5.8, H-1′); 8.08 (bq, 1 H, J = 4.7, NH); 8.78 (s, 1 H, H-8); 8.84 (s, 1 H,
H-2). 13C NMR (125.7 MHz, DMSO-d6): 25.99 (CH3N); 38.87 (CH2-pur); 61.53 (CH2-5′);
70.60 (CH-3′); 73.82 (CH-2′); 85.96 (CH-4′); 87.86 (CH-1′); 133.47 (C-5); 144.75 (CH-8);
150.79 (C-4); 151.91 (CH-2); 156.36 (C-6); 168.23 (CO). IR (CCl4): 3317, 2928, 1657, 1602,
20
1409, 1336, 1210, 1154. [α]D –35.2 (c 3.29, H2O).
6-[(Dimethylcarbamoyl)methyl]-9-(β-D-ribofuranosyl)-9H-purine (8h ). Prepared from purin e 8d
(340 m g, 0.5 m m ol) an d Et3N·3HF (408 µl, 2.5 m m ol) in THF (3 m l). Product was
lyoph ilized to give 153 m g (91%) of 8h as wh ite solid. MS (FAB): 338 (30, M + 1), 241 (85),
157 (50), 93 (100). HRMS (FAB): for C14H20N5O5 calculated 338.1464, foun d 338.1474.
1H NMR (499.8 MHz, DMSO-d6): 2.85 an d 3.11 (2 × s, 2 × 3 H, CH3N); 3.57 (ddd, 1 H, Jgem
=
12.1, J5′b,OH = 6.0, J5′b,4′ = 4.1, H-5′b); 3.69 (ddd, 1 H, Jgem = 12.1, J5′a,OH = 5.2, J5′a,4′ = 4.1,
H-5′a); 3.98 (td, 1 H, J4′,5′ = 4.1, J4′,3′ = 3.6, H-4′); 4.19 (td, 1 H, J3′,OH = J3′,2′ = 4.9, J3′,4′ = 3.6,
H-3′); 4.21 (s, 2 H, CH2-pur); 4.66 (ddd, 1 H, J2′,OH = 6.1, J2′,1′ = 5.8, J2′,3′ = 4.9, H-2′); 5.12
(dd, 1 H, JOH,5′ = 6.0, 5.2, OH-5′); 5.25 (d, 1 H, JOH,3′ = 4.9, OH-3′); 5.56 (d, 1 H, JOH,2′ = 6.1,
OH-2′); 6.03 (d, 1 H, J1′,2′ = 5.8, H-1′); 8.77 (s, 1 H, H-8); 8.84 (s, 1 H, H-2). 13C NMR
(125.7 MHz, DMSO-d6): 35.17 an d 37.52 (CH3N); 38.06 (CH2-pur); 61.55 (CH2-5′); 70.61
(CH-3′); 73.77 (CH-2′); 85.98 (CH-4′); 87.84 (CH-1′); 133.43 (C-5); 144.67 (CH-8); 150.67
(C-4); 151.87 (CH-2); 156.69 (C-6); 168.23 (CO). IR (CCl4): 3409, 2927, 1637, 1600, 1403,
20
1336, 1211, 1056. [α]D –40.0 (c 3.86, H2O).
6-[(Piperidine-1-carbonyl)methyl]-9-(β-D-ribofuranosyl)-9H-purine (9h ). Prepared from purin e
9d (525 m g, 0.73 m m ol) an d Et3N·3HF (596 µl, 3.65 m m ol) in THF (3 m l). Product was
lyoph ilized to give 270 m g (98%) of 9h as a wh ite solid. MS (FAB): 400 (100, M + Na), 378
(20, M + H). HRMS (FAB): for C17H24N5O5 calculated 378.1772, foun d 378.1770. 1H NMR
(400 MHz, DMSO-d6): 1.42 an d 1.49 (2 × m , 2 × 2 H, H-3,5-pip); 1.57 (m , 2 H, H-4-pip); 3.43
an d 4.52 (2 × t, 2 × 2 H, J = 5.4, H-2,6-pip); 3.58 (ddd, 1 H, Jgem = 12.0, J5′b,OH = 5.9, J5′b,4′
4.2, H-5′b); 3.67 (ddd, 1 H, Jgem = 12.0, J5′a,OH = 5.2, J5′a,4′ = 4.2, H-5′a); 3.98 (q, 1 H, J4′,5′
=
=
4.2, 4.1, J4′,3′ = 3.6, H-4′); 4.18 (td, 1 H, J3′,OH = 4.9, J3′,2′ = 4.9, J3′,4′ = 3.4, H-3′); 4.20 (s, 2 H,
CH2-pur); 4.66 (q, 1 H, J2′,OH = 5.9, J2′,1′ = 5.8, J2′,3′ = 4.9, H-2′); 5.11 (t, 1 H, JOH,5′ = 5.5,
OH-5′); 5.23 (d, 1 H, JOH,3′ = 4.9, OH-3′); 5.54 (d, 1 H, JOH,2′ = 5.9, OH-2′); 6.02 (d, 1 H,
J1′,2′ = 5.8, H-1′); 8.77 (s, 1 H, H-8); 8.84 (s, 1 H, H-2). 13C NMR (100.6 MHz, DMSO-d6):
23.87 (CH2-4-pip); 25.15 an d 25.85 (CH2-3,5-pip); 37.69 (CH2-pur); 42.05 an d 46.42
Collect. Czech. Chem. Commun. 2009, Vol. 74, Nos. 7–8, pp. 1035–1059