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Can. J. Chem. Vol. 89, 2011
158.03 (C-2) ppm. MS (ESI) m/z (%): 365 (100) [M + H]+.
Anal. calcd for C14H17N6O4P (364.3): C 46.16, H 4.70, N
23.07; found: C 46.29, H 4.72, N 3.04.
2,6-Diamino-8-(2,4-difluorophenyl)-9-[2-
(phosphonomethoxy)ethyl]purine (3h)
Method E gave a colourless solid; yield: 84%; mp >
1
250 8C. H NMR (500 MHz, D2O) d: 3.61 (d, JH,P = 8.6,
2,6-Diamino-8-vinyl-9-[2-(phosphonomethoxy)ethyl]purine
(3d)
2H, CH2P), 3.86 (t, Jvic = 5.7, 2H, CH2O), 4.22 (t, Jvic
=
5.7, 2H, CH2N), 4.59 (bs, 2H, NH2-2), 5.68 (bs, 2H, NH2-
6), 6.91 (ddd, J3’,F = 8.2, J3’,F = 8.0, J3’,5’) = 1.5, 1H, H-3’),
7.04 (ddd, J5’,F = 8.2, J5’,6’ = 7.6, J3’,5’ = 1.5, 1H, H-5’), 7.72
(ddd, J5’,6’ = 7.6, J6’,F = 5.0, 1H, H-6) ppm. 13C NMR
(125.8 MHz, D2O) d: 43.45 (CH2N), 65.18 (d, JC,P = 167,
CH2P), 70.94 (d, JC,P = 13.0, CH2O), 102.63 (C-3’), 112.07
(C-5), 114.23 (C-5’), 119.69 (C-1’), 132.85 (C-6’), 154.90
(C-8), 156.67 (C-4), 157.82 (C-6), 159.91 (C-2’), 162.36 (C-
4’), 162.99 (C-2) ppm. MS (ESI) m/z (%): 401 (100) [M + H]+.
Method E gave a colourless solid; yield: 69%; mp >
1
250 8C. H NMR (400 MHz, D2O) d: 3.78 (d, JH,P = 8.3,
2H, CH2P), 3.86 (t, Jvic = 5.2, 2H, CH2O), 4.24 (t, Jvic
5.2, 2H, CH2N), 5.48 (d, Jcis = 4.8, 1H, CH2-2’trans), 6.33
(d, Jtrans = 17.1, 1H, CH2-2’cis), 6.70 (dd, Jtrans = 17.1, Jcis
=
=
4.8, 1H, CH-1’) ppm. 13C NMR (125.8 MHz, D2O) d: 41.80
(CH2N), 72.22 (d, JC,P = 157, CH2P), 72.42 (d, JC,P = 11.0,
CH2O), 113.65 (C-5), 120.63 (C-2’), 123.29 (C-1’), 146.07
(C-8), 152.61 (C-4), 154.96 (C-6), 159.73 (C-2) ppm. MS
(ESI) m/z (%): 337 (30) [M + Na]+, 315 (100) [M + H]+.
Anal. calcd for C10H15N6O4P (314.2): C 38.22, H 4.81, N
26.74; found: C 38.36, H 4.78, N 26.75.
2,6-Diamino-8-(thien-3-yl)-9-[2-
(phosphonomethoxy)ethyl]purine (3i)
Method E afforded a colourless solid; yield: 76%; mp >
1
250 8C. H NMR (400 MHz, D2O) d: 3.62 (d, JH,P = 8.7,
2,6-Diamino-8-allyl-9-[2-(phosphonomethoxy)ethyl]purine
(3e)
2H, CH2P), 3.96 (t, Jvic = 5.6, 2H, CH2O), 4.34 (t, Jvic
5.6, 2H, CH2N), 4.85 (bs, 2H, NH2-2), 5.51 (bs, 2H, NH2-
6), 7.22 (dd, J5’,4’ = 7.5, J5’,2’ = 1.5, 1H, H-5’), 7.74 (dd, J4’,5’
7.5, J4’,2’ = 2.9, 1H, H-4’), 8.01 (dd, J2’,4’ = 5.0, J2’,5’ = 1.5,
H-2’) ppm. 13C NMR (125.8 MHz, D2O) d: 42.95 (CH2N),
66.21 (d, JC,P = 165, CH2P), 70.26 (d, JC,P = 12.0, CH2O),
113.47 (C-5), 126.38 (C-2’), 127.60 (C-4’), 128.19 (C-5’),
135.51 (C-1’), 154.28 (C-8), 157.74 (C-4), 160.19 (C-6),
164.86 (C-2) ppm. MS (ESI) m/z (%): 371 (100) [M + H]+.
=
Method E afforded a colourless solid; yield: 68%; mp >
=
1
250 8C. H NMR (400 MHz, D2O) d: 3.35 (d, Jvic = 6.3,
2H, CH2-1’), 3.72 (d, JH,P = 8.4, 2H, CH2P), 3.86 (t, Jvic
=
5.4, 2H, CH2O), 4.26 (t, Jvic = 5.4, 2H, CH2N), 5.30 (dq,
J3’cis1’ = Jgem = 1.4, Jtrans = 17.7, 1H, CH2-3’cis), 6.02 (ddt,
Jtrans = 17.7, Jcis = 8.3, Jvic = 6.3, 1H, CH-2’) ppm. 13C
NMR (125.8 MHz, D2O) d: 40.15 (C-1’), 41.59 (CH2N),
69.11 (d, JC,P = 155, CH2P), 71.84 (d, JC,P = 10.0, CH2O),
113.74 (C-5), 116.45 (C-3’), 138.26 (C-2’), 148.64 (C-8),
151.72 (C-4), 156.27 (C-6), 159.53 (C-2) ppm. MS (ESI) m/z
(%): 351 (10) [M + Na]+, 329 (100) [M + H]+. Anal. calcd
for C11H17N6O4P (328.2): C 40.25, H 5.22, N 25.60; found:
C 40.15, H 5.19, N 25.64.
2,6-Diamino-8-(2-phenylvinyl)-9-[2-
(phosphonomethoxy)ethyl]purine (3j)
Method E gave a colourless solid; yield: 65%; mp >
1
250 8C. H NMR (500 MHz, D2O) d: 3.59 (d, JH,P = 8.5,
2H, CH2P), 4.08 (t, Jvic = 5.7, 2H, CH2O), 4.34 (t, Jvic
=
5.7, 2H, CH2N), 5.36 (bs, 2H, NH2-2), 6.44 (bs, 2H, NH2-
6), 6.89 (d, Jtrans = 15.5, 1H, H-2’), 7.04 (d, Jtrans = 15.5,
1H, H-1’), 7.44–7.51 (m, 3H, H-m, p-Ph), 7.83 (m, 2H, H-
o-Ph) ppm. 13C NMR (125.8 MHz, D2O) d: 42.15 (CH2N),
66.32 (d, JC,P = 161, CH2P), 71.65 (d, JC,P = 12.0, CH2O),
112.92 (C-1’), 114.07 (C-5), 128.39 (CH-m-Ph), 130.22
(CH-o-Ph), 131.21 (C-i-Ph), 134.58 (C-2’), 153.06 (C-8),
153.80 (C-4), 157.19 (C-6), 160.25 (C-2) ppm. MS (ESI) m/z
(%): 391 (100) [M + H]+.
2,6-Diamino-8-(thien-2-yl)-9-[2-
(phosphonomethoxy)ethyl]purine (3f)
Method E gave a pale yellow solid; yield: 75%; mp >
1
250 8C. H NMR (400 MHz, D2O) d: 3.71 (d, JH,P = 8.5,
2H, CH2P), 3.99 (t, Jvic = 5.5, 2H, CH2O), 4.41 (t, Jvic
5.5, 2H, CH2N), 7.13 (dd, J4’,5’ = 5.0, J4’,3’ = 3.7, 1H, H-4’),
7.39 (dd, J5’,4’ = 5.0, J5’,3’ = 0.7, 1H, H-5’), 7.62 (dd, J3’,4’
3.7, J3’,5’ = 0.7, 1H, H-3’) ppm. 13C NMR (125.8 MHz, D2O)
d: 41.35 (CH2N), 69.72 (d, JC,P = 156, CH2P), 70.62 (d, JC,P
10.0, CH2O), 113.51 (C-5), 127.52 (CH-5’), 127.52 (CH-4’),
128.04 (CH-3’), 131.25 (CH-2’), 141.22 (C-8), 153.95 (C-4),
155.36 (C-6), 159.50 (C-2) ppm. MS (ESI) m/z (%): 371
(100) [M + H]+. Anal. calcd for C12H15N6O4PS (370.3): C
38.92, H 4.08, N 22.69; found: C 39.20, H 4.15, N 22.74.
=
=
=
2,6-Diamino-8-(propene-2-yl)-9-[2-
(phosphonomethoxy)ethyl]purine (3k)
Method E gave a pale yellow solid; yield: 69%; mp >
1
250 8C. H NMR (400 MHz, D2O) d: 2.42 (s, 3H, CH3-8),
3.71 (d, JH,P = 8.6, 2H, CH2P), 4.19 (t, Jvic = 5.6, 2H, CH2O),
4.35 (t, Jvic = 5.6, 2H, CH2N), 5.41 and 5.45 (2 Â s, 2H, CH2-
2’) ppm. 13C NMR (125.8 MHz, D2O) d: 22.19 (CH3-8), 42.97
(CH2N), 70.87 (d, JC,P = 8.0, CH2O), 71.47 (d, JC,P = 153,
CH2P), 112.85 (C-5), 119.23 (C-2’), 134.41 (C-1’), 148.73
(C-8), 153.16 (C-4), 155.61 (C-6), 159.70 (C-2) ppm. MS
(ESI) m/z (%): 350 (5) [M + Na]+, 329 (100) [M + H]+.
2,6-Diamino-8-[4-(trifluoromethyl)phenyl]-9-[2-
(phosphonomethoxy)ethyl]purine (3g)
Method E afforded a colourless solid; yield: 82%; mp >
1
250 8C. H NMR (500 MHz, CDCl3) d: 3.70 (d, JH,P = 8.6,
2H, CH2P), 4.12 (t, Jvic = 5.7, 2H, CH2O), 4.36 (t, Jvic = 5.7,
2H, CH2N), 4.51 (bs, 2H, NH2-2), 5.68 (bs, 2H, NH2-6),
7.56 (d, J = 8.2, 2H, H-3’,5’), 8.01 (d, J = 8.2, 2H, H-2’,6’)
ppm. 13C NMR (125.8 MHz, D2O) d: 42.92 (CH2N), 65.73
(d, JC,P = 166, CH2P), 70.36 (d, JC,P = 12.0, CH2O), 112.95
(C-5), 126.32 (CH-m-PH), 127.53 (CH-o-Ph), 131.22 (CF3),
132.18 (C-i-Ph), 154.23 (C-8), 157.47 (C-4), 159.01 (C-6),
162.73 (C-2) ppm. MS (ESI) m/z (%): 455 (100) [M + Na]+.
2,6-Diamino-8-(benzyl)-9-[2-
(phosphonomethoxy)ethyl]purine (3l)
Method E afforded a pale yellow solid; yield: 82%; mp >
1
250 8C. H NMR (500 MHz, D2O) d: 3.58 (d, JH,P = 8.3,
2H, CH2P), 4.04 (s, 2H, H-1’), 4.00 (t, Jvic = 5.8, 2H,
CH2O), 4.36 (t, Jvic = 5.8, 2H, CH2N), 5.22 (bs, 2H, NH2-
Published by NRC Research Press