Vol. 29, No. 1, 2018
Medeiros et al.
165
Diisopropyl 5‑(5‑cyano‑3‑methyl‑1‑phenyl‑
H ‑pyrazolo[3, 4‑b ]pyr idin‑4‑ylamino)pentyl
Diisopropyl 3‑(5‑cyano‑1,3‑diphenyl‑1H‑pyrazolo
[3,4‑b]pyridin‑4‑ylamino)propyl phosphoramidate (16b)
Yield 68%; pale brown solid; mp 112-115 °C; IR (KBr)
1
phosphoramidate (15d)
-1
Yield 73%; pale brown solid; mp 163-165 °C; IR (KBr)
ν / cm 3392 (νN−H), 1230 (νP=O), 985 (νP−O), 2210
-1
1
ν / cm 3334 (νN−H), 1232 (νP=O), 987 (νP−O), 2208
(νC≡N); H NMR (500 MHz, CDCl ) d 1.28 and 1.29 (2d,
3
1
(
νC≡N); H NMR (500 MHz, CDCl ) d 1.28 and 1.27 (2d,
12H, J 5.8 Hz), 1.60-1.63 (m, 2H), 2.71-2.74 (m, 1H), 2.93-
2.96 (m, 2H), 3.74-3.77 (m, 2H), 4.51 (dhep, 2H, J 6.0,
7.5 Hz), 5.48 (t, 1H, J 4.8 Hz), 7.31-7.35 (m, 1H), 7.50-7.65
3
12H, J 6.1 Hz), 1.40-1.45 (m, 4H), 1.49-1.54 (m, 2H), 2.36
(dt, 1H, J 7.3, 10.8 Hz), 2.70 (s, 3H), 2.88-2.92 (m, 2H),
13
3
5
.82 (dt, 2H, J 6.1, 7.1 Hz), 4.55 (dhep, 2H, J 6.2, 7.6 Hz),
.40 (t, 1H, J 5.8 Hz), 7.29 (t, 1H, J 7.4 Hz), 7.45 (t, 2H,
(m, 5H), 8.11 (m, 2H) , 8.40 (s, 1H); C NMR (75 MHz,
CDCl ) d 23.7 (d, J 4.1 Hz), 26.8, 28.3 (d, J6.2 Hz), 40.7,
3
1
3
J 8.4 Hz), 8.00 (d, 2H, J 7.5 Hz), 8.31 (s, 1H); C NMR
43.7, 70.6 (d, J 5.4 Hz), 82.8, 102.9, 119.5, 122.1, 128.9,
3
1
(
75 MHz, CDCl ) d 15.3, 23.3 (d, J 4.5 Hz), 23.0, 29.5, 30.8
129.2, 129.7, 138.5, 145.1, 150.8, 155.7; P{H} NMR
3
(
d, J 6.2 Hz), 40.7, 43.9, 70.2 (d, J 5.8 Hz), 82.5, 103.8,
19.3, 121.4, 126.1, 128.6, 138.2, 140.7, 151.0, 155.3;
(202 MHz, CDCl ) d 7.43 (s); HRMS (ESI) m/z, calcd.
3
+
1
for C H N O P: 533.2430 [M + H] , found: 533.2429.
28
33
6
3
31
P{H} NMR (202 MHz, CDCl ) d 7.66 (s); HRMS (ESI)
3
+
m/z, calcd. for C H N O P: 499.2587 [M + H] , found:
4
Diisopropyl 4‑(5‑cyano‑1,3‑diphenyl‑1H‑pyrazolo
[3,4‑b]pyridin‑4‑ylamino)butyl phosphoramidate (16c)
Yield 70%; pale brown solid; mp 85-89 °C; IR (KBr)
25
35
6
3
99.2573.
-1
Diisopropyl 6‑(5‑cyano‑3‑methyl‑1‑phenyl‑
H ‑ py r a zo l o [ 3 , 4 ‑ b ] py r i d i n ‑ 4 ‑ y l a m i n o ) h ex y l
ν / cm 3417 (νN−H), 1226 (νP=O), 981 (νP−O), 2210
1
1
(νC≡N); H NMR (300 MHz, CDCl ) d 1.22 and 1.26 (2d,
3
phosphoramidate (15e)
12H, J 5.8 Hz), 1.33-1.37 (m, 2H), 1.47-1.56 (m, 2H),
2.32 (dt, 1H, J 7.2, 9.0 Hz), 2.75-2.80 (m, 2H), 3.63 (dt,
1H, J 5.7, 7.0 Hz), 4.46 (dhep, 2H, J6.1, 7.5 Hz), 5.42 (t,
1H, J 5.5 Hz), 7.29 (d, 1H, J 6.9 Hz), 7.44-7.62 (m, 7H),
Yield 72%; pale brown solid; mp 165-168 °C; IR (KBr)
-1
ν / cm 3403 (νN−H), 1230 (νP=O), 1004 (νP−O), 2204
1
(
νC≡N); H NMR (500 MHz, CDCl ) d 1.30 and 1.32 (2d,
3
1
3
12H, J 5.9 Hz), 1.47-1.51 (m, 6H), 1.78-1.81 (m, 2H), 2.46
8.07 (d, 2H, J 7.5 Hz), 8.36 (s, 1H); C NMR (75 MHz,
(dt, 1H, J 7.2, 9.0 Hz), 2.73 (s, 3H), 2.91 (dt, 2H, J 6.9,
CDCl ) d 23.7 (d, J 4.1 Hz), 26.8, 28.3 (d, J6.2 Hz), 40.7,
3
9
5
.2 Hz), 3.82-3.86 (m, 2H), 4.54 (dhep, 2H, J 6.2, 7.5 Hz),
.44 (t, 1H J 5.5 Hz), 7.31 (t, 1H, J 7.4 Hz), 7.49 (t, 2H,
43.7, 70.6 (d, J 5.4 Hz), 82.8, 102.9, 119.5, 122.1, 128.9,
129.2, 129.7, 138.5, 145.1, 150.8, 155.7; P{H} NMR
3
1
13
J 8.5 Hz), 8.06 (d, 2H, J 8.6 Hz), 8.34 (s, 1H); C NMR
125 MHz, CDCl ) d 15.6, 23.6 (d, J 4.5 Hz), 25.9, 26.0,
(202 MHz, CDCl ) d 7.43 (s); HRMS (ESI) m/z, calcd.
3
+
(
for C H N O P: 547.2587 [M + H] , found: 547.2590.
3
29 35
6
3
3
1
1
0.1, 31.3 (d, J 6.5 Hz), 41.1, 44.1, 70.4 (d, J 5.2 Hz), 82.8,
04.1, 119.5, 121.6, 126.3, 128.9, 138.5, 140.9, 151.3,
Diisopropyl 5‑(5‑cyano‑1,3‑diphenyl‑1H‑pyrazolo
[3,4‑b]pyridin‑4‑ylamino)pentyl phosphoramidate (16d)
Yield 69%; pale brown solid; mp 90-93 °C; IR (KBr)
3
1
55.5; P{H} NMR (202 MHz, CDCl ) d 7.68 (s); HRMS
3
+
(
ESI) m/z, calcd. for C H N O P: 513.2743 [M + H] ,
2
6
37
6
3
-1
found: 513.2723.
ν / cm 3400 (νN−H), 1232 (νP=O), 985 (νP−O), 2212
1
(
νC≡N); H NMR (300 MHz, CDCl ) d 1.27 and 1.29 (2d,
3
Diisopropyl 2‑(5‑cyano‑1,3‑diphenyl‑1H‑pyrazolo
12H, J 4.5 Hz), 1.10-1.17 (m, 4H), 1.43-1.48 (m, 2H),
2.20-2.25 (m, 1H), 2.77 (dt, 2H, J 7.1, 9.6 Hz), 3.66 (dt,
2H, J 5.7, 6.8 Hz), 4.48 (dhep, 2H, J6.1, 7.4 Hz), 5.43 (t,
[
3,4‑b]pyridin‑4‑ylamino)ethyl phosphoramidate (16a)
Yield 69%; pale brown solid; mp 108-110 °C; IR
-
1
(
KBr) ν / cm 3411 (νN−H), 1012 (νP=O), 988 (νP−O),
1H, J 5.5 Hz), 6.94 (s, 1H), 7.45-7.56 (m, 6H), 8.09 (m,
1
13
2
1
3
4
208 (νC≡N); H NMR (300 MHz, CDCl ) d 1.19 and
2H), 8.37 (s, 1H); C NMR (75 MHz, CDCl ) d 23.6 (d,
3
3
.21 (2d, 12H, J 6.1 Hz), 2.50 (dt, 1H, J 6.9, 8.7 Hz),
.12 (dt, 2H, J 6.4, 12.8 Hz), 3.81 (dt, 2H, J 6.2, 8.2 Hz),
.48 (dhep, 2H, J6.2, 7.5 Hz), 5.75 (t, 1H, J 6.2 Hz), 7.33
J 4.6 Hz), 27.4, 28.4 (d, J 5.8 Hz), 40.7, 41.0, 43.9, 70.7 (d,
J 5.4 Hz), 82.8, 104.1, 119.6, 121.7, 126.4, 128.9, 138.5,
3
1
141.0, 151.3, 155.6; P{H} NMR (121 MHz, CDCl3)
(
8
t, 1H, J 7.7 Hz), 7.50-7.59 (m, 5H), 7.66-7.68 (m, 2H),
.10 (d, 2H, J 7.5 Hz), 8.40 (s, 1H); C NMR (75 MHz,
d 7.18 (s); HRMS (ESI) m/z, calcd. for C H N O P:
561.2743 [M + H] , found: 561.2745.
3
0
37
6
3
13
+
CDCl ) d 23.4 (d, J 4.8 Hz), 40.9, 44.4 (d, J 4.4 Hz), 70.91
3
(
1
d, J 5.7 Hz), 104.6, 114.6, 119.5, 122.0, 128.0, 129.0,
30.0, 130.5, 138.3, 142.5, 150.7, 151.2; P{H} NMR
Diisopropyl 6‑(5‑cyano‑1,3‑diphenyl‑1H‑pyrazolo[3,4‑b]
pyridin‑4‑ylamino)hexyl phosphoramidate (16e)
3
1
(
202 MHz, CDCl ) d 6.93 (s); HRMS (ESI) m/z, calcd.
Yield 67%; pale brown solid; mp 83-85 °C; IR (KBr)
ν / cm 3404 (νN−H), 1224 (νP=O), 979 (νP−O), 2214
3
+
-1
for C H N O P: 519.2274 [M + H] , found: 519.2278.
2
7
31
6
3