M. Kucharˇ, R. Pohl, I. Votruba, M. Hocek
FULL PAPER
134 (35), 119 (18), 96 (25), 83 (25). HRMS: calcd. for C17H23N5O
CH2O-THP), 4.17 (2×m, 2 H, CH2O-THP), 5.69 (d, Jtrans = 13.0 Hz,
1 H, =CH-pur), 5.73 (dd, J = 9.8, 3.0 Hz, 1 H, CHO-THP), 8.06 (s,
1 H, 8-H), 8.26 (d, Jtrans = 13.0 Hz, 1 H, =CH-N), 8.55 (s, 1 H, 2-
H) ppm. 13C NMR (100.4 MHz, CDCl3): δ = 22.88 (CH2-THP),
24.90 (CH2-THP), 31.79 (CH2-THP), 42.44 (CH3), 68.75 (CH2O-
THP), 81.51 (CHO-THP), 90.38 (=CH-pur), 127.54 (C-5), 138.61
(CH-8), 149.03 (C-4), 149.56 (=CH-N), 152.53 (CH-2), 157.50 (C-6)
ppm. EI-MS: m/z (rel.%) = 273 (48) [M]+, 189 (100), 174 (50), 162
(32), 147 (40), 134 (30), 119 (18), 96 (25). HRMS: calcd. for
313.1902; found 313.1891. IR (CHCl ): ν = 2947, 1623, 1586, 1497,
˜
3
1441, 1399, 1362, 1246, 1058, 1045, 979, 915, 816, 648 cm–1.
(E)-6-[2-(Morpholine-4-yl)vinyl]-9-(tetrahydropyran-2-yl)purine (10b):
Reaction time 2 d, yield 45%, yellow crystal, m.p. 171–173 °C. 1H
NMR (500 MHz, CDCl3): δ = 1.61–1.84 (2×m, 6 H, CH2-THP),
2.01–2.15 (2×m, 6 H, CH2-THP), 3.40 (m, 4 H, CH2-N), 3.77 (m, 4
H, CH2-O), 3.79 (td, J = 11.7, 2.5 Hz, 1 H, bCH2O-THP), 4.18 (ddt,
J = 11.7, 4.4, 1.9 Hz, 1 H, aCH2O-THP), 5.74 (dd, J = 10.2, 2.6 Hz,
1 H, CHO-THP), 5.88 (d, Jtrans = 13.3 Hz, 1 H, =CH-pur), 8.08 (s,
1 H, 8-H), 8.17 (d, Jtrans = 13.3 Hz, 1 H, =CH-N), 8.59 (s, 1 H, 2-
H) ppm. 13C NMR (125.8 MHz, CDCl3): δ = 22.87 (CH2-THP),
24.90 (CH2-THP), 31.80 (CH2-THP), 48.74 (CH2-N), 66.31 (CH2-
O), 68.79 (CH2O-THP), 81.59 (CHO-THP), 91.68 (=CH-pur), 128.00
(C-5), 139.13 (CH-8), 148.21 (=CH-N), 149.28 (C-4), 152.48 (CH-2),
157.13 (C-6) ppm. EI-MS: m/z (rel.%) = 315 (60) [M]+, 230 (100),
201 (45), 186 (17), 174 (28), 147 (45), 134 (25), 119 (13), 85 (20).
HRMS: calcd. for C16H21N5O2 315.1695; found 315.1689. IR
C H N O 273.1589; found 273.1583. IR (CHCl ): ν = 2952, 1633,
˜
14 19
5
3
1587, 1413, 1389, 1230, 1085, 1045, 980, 915, 665, 648 cm–1.
(Z)- and (E)-6-[2-(Cyclohexylamino)vinyl]-9-(tetrahydropyran-2-yl)pu-
rine (12f): Reaction time 2 d, yield 73%, red oil. 1H NMR (400 MHz,
CDCl3): δ = 1.20–1.49 [3×m, 32 H, CH2-chex-(Z)+(E) and CH2-
THP-(Z)+(E)], 1.58–1.86 [3×m, 32 H, CH2-chex-(Z)+(E) and CH2-
THP-(Z)+(E)], 1.97–2.16 [3×m, 32 H, CH2-chex-(Z)+(E) and CH2-
THP-(Z)+(E)], 3.15 [m, 1 H, CHNH-(Z)], 3.38 [m, 1 H, CHNH-(E)],
3.79 [td, J = 11.7, 2.5 Hz, 2 H, bCH2O-THP-(Z)+(E)], 4.17 [ddt, J
= 11.7, 4.5, 1.8 Hz, 2 H, aCH2O-THP-(Z)+(E)], 4.65 [br. m, 1 H,
NH-(E)], 5.63 [d, Jcis = 8.1 Hz, 1 H, =CH-pur-(Z)], 5.73 [dd, J = 9.8,
2.9 Hz, 2 H, CHO-THP-(Z)+(E)], 5.88 [d, Jtrans = 13.4 Hz, 1 H,
=CH-pur-(E)], 6.92 [dd, JCH,NH = 12.9 Hz, Jcis = 8.1 Hz, 1 H, =CH-
N-(Z)], 8.06 [s, 1 H, 8-H-(Z)+(E)], 8.35 [dd, Jtrans = 13.4 Hz, JCH,NH
= 8.8 Hz, 1 H, =CH-N-(E)], 8.57 [s, 1 H, 2-H-(E)], 8.62 [s, 1 H, 2-
H-(Z)], 9.62 [br. m, 1 H, NH-(Z)] ppm. 13C NMR [100.6 MHz,
CDCl3, (Z) isomer only]: δ = 22.88 (CH2-THP), 24.65 (CH2-chex),
24.91 (CH2-THP), 235.50 (CH2-chex), 31.88 (CH2-THP), 34.37
(CH2-chex), 56.97 (CHNH), 68.74 (CH2O-THP), 81.50 (CHO-
THP), 85.54 (=CH-pur), 127.39 (C-5), 138.38 (CH-8), 146.78 (=CH-
N), 147.85 (C-4), 151.83 (CH-2), 158.27 (C-6) ppm. EI-MS: m/z
(rel.%) = 327 (30) [M]+, 243 (100), 214 (8), 200 (30), 186 (18), 173
(12), 160 (34), 147 (30), 134 (28), 119 (18), 97 (20), 83 (16). HRMS:
(CHCl ): ν = 2974, 2862, 1626, 1588, 1572, 1429, 1170, 1116, 1085,
˜
3
1045, 980, 914, 867, 821, 648 cm–1.
(E)-6-[2-(Dibutylamino)vinyl]-9-(tetrahydropyran-2-yl)purine (10c): Re-
action time 2 d, yield 81%, brown oil. 1H NMR (400 MHz, CDCl3):
δ = 0.95 (t, Jvic = 7.3 Hz, 6 H, CH3CH2CH2CH2), 1.36 (m, 4 H,
CH3CH2CH2CH2), 1.58–1.87 (m, 7 H, CH3CH2CH2CH2 and CH2-
THP), 1.99–2.14 (m,
CH3CH2CH2CH2), 3.79 (td, J = 11.7, 2.5 Hz, 1 H, bCH2O-THP),
4.17 (ddt, J = 11.7, 4.3, 1.4 Hz, 1 H, aCH2O-THP), 5.71 (d, Jtrans
3
H, CH2-THP), 3.28 (m,
4
H,
=
13.1 Hz, 1 H, =CH-pur), 5.73 (dd, J = 9.8, 2.8 Hz, 1 H, CHO-THP),
8.04 (s, 1 H, 8-H), 8.30 (br. d, Jtrans = 13.1 Hz, 1 H, =CH-N), 8.53
(s, 1 H, 2-H) ppm. 13C NMR (100.6 MHz, CDCl3): δ = 13.84
(CH3CH2CH2CH2), 20.13 (CH3CH2CH2CH2), 22.90 (CH2-THP),
24.93
(CH2-THP),
28.80
(CH3CH2CH2CH2),
31.59
calcd. for C H N O 327.2059; found 327.2047. IR (CHCl ): ν =
˜
18 25
5
3
(CH3CH2CH2CH2), 31.86 (CH2-THP), 47.94 (CH3CH2CH2CH2),
56.03 (CH3CH2CH2CH2), 68.76 (CH2O-THP), 81.49 (CHO-THP),
89.64 (=CH-pur), 127.34 (C-5), 138.41 (CH-8), 148.73 (=CH-N),
148.91 (C-4), 152.57 (CH-2), 157.87 (C-6) ppm. EI-MS: m/z (rel.%)
= 357 (96) [M]+, 314 (10), 273 (100), 256 (18), 244 (65), 244 (65), 230
(70), 216 (65), 174 (26), 160 (22), 149 (47), 134 (45), 85 (20). HRMS:
2936, 2858, 1632, 1585, 1450, 1327, 1085, 1045, 975, 913, 876, 811,
667 cm–1.
(Z)- and (E)-6-[2-(Benzylamino)vinyl]-9-(tetrahydropyran-2-yl)purine
(12g): Reaction time 1 d, yield 85%, brown oil. 1H NMR (400 MHz,
CDCl3): δ = 1.57–1.86 [2 ×m, 12 H, CH2-THP-(Z)+(E)], 1.99–2.14
[2 ×m, 12 H, CH2-THP-(Z)+(E)], 3.78 [2×m, 2×2 H, CH2O-THP-
(Z)+(E)], 4.43 [d, JCH2,NH = 5.4 Hz, 2 H, CH2NH-(E)], 4.51 [d,
JCH2,NH = 6.0 Hz, 2 H, CH2NH-(Z)],4.96 [br. m, 1 H, NH-(E)], 5.72–
5.76 [m, 3 H, =CH-pur-(Z) and CHO-THP-(Z)+(E)], 5.97 [d, Jtrans
calcd. for C H N O 357.2529; found 357.2524. IR (CHCl ): ν =
˜
20 31
5
3
2961, 2934, 1622, 1584, 1429, 1369, 1085, 1045, 980, 914, 814, 648
cm–1.
(E)-6-[2-(Diethylamino)vinyl]-9-(tetrahydropyran-2-yl)purine (10d): Re-
1
= 13.4 Hz, 1 H, =CH-pur-(E)], 6.91 [dd, JCH,NH = 12.5 Hz, Jcis
=
action time 1 d, yield 81%, red oil. H NMR (500 MHz, CDCl3): δ
8.2 Hz, 1 H, =CH-N-(Z)], 7.26–7.39 [m, 10 H, Ph-(Z)+(E)], 8.09 [s,
1 H, 8-H-(Z)+(E)], 8.49 [dd, Jtrans = 13.3 Hz, JCH,NH = 8.0 Hz, 1 H,
=CH-N-(E)], 8.60 [s, 1 H, 2-H-(E)], 8.62 [s, 1 H, 2-H-(Z)], 9.88 [br.
m, 1 H, NH-(Z)] ppm. 13C NMR [100.6 MHz, CDCl3, (Z) isomer
only]: δ = 22.87 (CH2-THP), 24.90 (CH2-THP), 31.84 (CH2-THP),
52.53 (CH2NH), 68.75 (CH2O-THP), 81.57 (CHO-THP), 86.88
(=CH-pur), 126.99 (CH-o-Ph), 127.41 (CH-p-Ph), 127.65 (C-5),
128.71 (CH-m-Ph), 138.79 (CH-8), 139.22 (C-i-Ph), 148.17 (C-4),
148.60 (=CH-N), 151.78 (CH-2), 158.17 (C-6) ppm. EI-MS: m/z
(rel.%) = 335 (28) [M]+, 251 (100), 234 (7), 195 (35), 160 (27), 147
(20), 135 (17), 117 (7), 106 (35), 91 (65), 85 (8). HRMS: calcd. for
= 1.25 (t, Jvic = 7.2 Hz, 6 H, CH3), 1.61–1.84 (2×m, 6 H, CH2-
THP), 2.00–2.14 (2×m, 6 H, CH2-THP), 3.37 (q, Jvic = 7.2 Hz, 4 H,
CH2-N), 3.79 (td, J = 11.7, 2.4 Hz, 1 H, bCH2O-THP), 4.17 (ddt, J
= 11.7, 4.2, 1.9 Hz, 1 H, aCH2O-THP), 5.73 (dd, J = 10.5, 2.6 Hz, 1
H, CHO-THP), 5.75 (d, Jtrans = 13.1 Hz, 1 H, =CH-pur), 8.05 (s, 1
H, 8-H), 8.28 (d, Jtrans = 13.1 Hz, 1 H, =CH-N), 8.54 (s, 1 H, 2-H)
ppm. 13C NMR (125.8 MHz, CDCl3): δ = 12.09 (CH3), 14.33 (CH3),
22.90 (CH2-THP), 24.93 (CH2-THP), 31.85 (CH2-THP), 42.27 (CH2-
N), 50.00 (CH2-N), 68.77 (CH2O-THP), 81.51 (CHO-THP), 89.38
(=CH-pur), 127.35 (C-5), 138.48 (CH-8), 147.75 (=CH-N), 148.90
(C-4), 152.50 (CH-2), 157.76 (C-6) ppm. EI-MS: m/z (rel.%) = 301
(42) [M]+, 217 (70), 202 (12), 188 (100), 174 (18), 160 (24), 147 (40),
134 (38), 119 (12), 84 (12). HRMS: calcd. for C16H23N5O 301.1902;
C H N O 335.1746; found 335.1739. IR (CHCl ): ν = 2952, 1635,
˜
19 21
5
3
1587, 1447, 1327, 1261, 1171, 1085, 1045, 977, 913, 876, 812, 699,
648 cm–1.
found 301.1889. IR (CHCl ): ν = 2978, 2868, 1623, 1569, 1430, 1360,
˜
3
1259, 1084, 1054, 981, 814, 648 cm–1.
(Z)- and (E)-6-[2-(Methylamino)vinyl]-9-(tetrahydropyran-2-yl)purine
(E)-6-[2-(Dimethylamino)vinyl]-9-(tetrahydropyran-2-yl)purine (10e): (12h): Reaction time 2 h, yield 94%, brown oil. 1H NMR (500 MHz,
Reaction time 4 d, yield 64%, white solid, m.p. 167–168 °C. 1H NMR
(400 MHz, CDCl3): δ = 1.60–1.85 (2×m, 6 H, CH2-THP), 2.00–2.15
(2×m, 6 H, CH2-THP), 3.05 (br. s, 6 H, CH3), 3.79 (2×m, 2 H,
CDCl3): δ = 1.58–1.84 [2×m, 12 H, CH2-THP-(Z)+(E)], 2.00–2.15
[2×m, 12 H, CH2-THP-(Z)+(E)], 2.96 [d, JCH3,NH = 5.2 Hz, 3 H,
CH3-(E)], 3.11 [d, JCH3,NH = 4.8 Hz, 3 H, CH3-(Z)], 3.79 [m, 2 H,
5092
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Eur. J. Org. Chem. 2006, 5083–5098