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QIN ET AL.
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6‐Benzyl‐2‐(4‐ethylpiperazin‐1‐yl)‐N‐(5‐methyl‐1H‐pyrazol‐3‐yl)‐
pyrimidin‐4‐amine (B2)
piperidine‐H). HRMS calcd. for C20H26N7, [M+H]+, 364.2250; found
364.2241.
Light yellow solid (0.04 g, 82.2% yield). 1H NMR (400 MHz, DMSO‐
d6) δ ppm: 12.00 (s, 1H, NH‐pyrazole), 9.32 (s, 1H, Ar‐NH‐Ar),
7.37–7.10 (m, 5H, Ph‐H), 6.15 (s, 1H, pyrazole‐H), 6.03 (s, 1H,
pyrimidine‐H), 3.72 (s, 2H, Ph‐CH2‐Ar), 3.31–3.33 (m, 4H, piperazine‐
H), 2.21–2.19 (s, 6H, N‐CH2 ‐Me and piperazine‐H), 1.29–1.06 (m, 3H,
CH3‐pyrazole), 0.89–0.80 (m, 3H, CH3 in Et). HRMS calcd. for
C21H28N7, [M+H]+, 378.2406; found 378.2398.
6‐Benzyl‐2‐(1,4‐diazepan‐1‐yl)‐N‐(5‐methyl‐1H‐pyrazol‐3‐yl)‐
pyrimidin‐4‐amine (B7)
Light yellow solid (0.04 g, 80.1% yield). 1H NMR (400 MHz, DMSO‐d6) δ
ppm: 11.89 (s, 1H, NH‐pyrazole), 9.33 (s, 1H, Ar‐NH‐Ar), 7.45–7.08 (m,
5H, Ph‐H), 6.14 (s, 2H, pyrazole‐H, and pyrimidine‐H), 3.96
(d, J = 6.0 Hz, 2H, Ph‐CH2‐Ar), 3.82 (t, J = 6.0 Hz, 2H, diazepane‐H), 3.72
(s, 2H, diazepane‐H), 3.21 (s, 2H, diazepane‐H), 3.05 (d, J = 7.1 Hz, 2H,
diazepane‐H), 2.19 (s, 3H, CH3), 2.06 (s, 2H, diazepane‐H). HRMS calcd.
for C20H26N7, [M+H]+, 364.2250; found 364.2246.
6‐Benzyl‐N‐(5‐methyl‐1H‐pyrazol‐3‐yl)‐2‐morpholinopyrimidin‐4‐
amine (B3)
Light yellow solid (0.03 g, 76.5% yield). 1H NMR (400 MHz, DMSO‐
d6) δ ppm: 11.83 (s, 1H, NH‐pyrazole), 9.27 (s, 1H, Ar‐NH‐Ar),
7.39–7.10 (m, 5H, Ph‐H), 6.20 (s, 1H, pyrazole‐H), 6.11 (s, 1H,
pyrimidine‐H), 3.71 (s, 2H, Ph‐CH2‐Ar), 3.71–3.64 (m, 8H,
morpholine‐H), 2.18 (s, 3H, CH3). HRMS calcd. for C19H24N6O, [M
+H]+, 351.1933; found 351.1928.
6‐Benzyl‐2‐(4‐methyl‐1,4‐diazepan‐1‐yl)‐N‐(5‐methyl‐1H‐pyrazol‐3‐
yl)pyrimidin‐4‐amine (B8)
Light yellow solid (0.03 g, 82% yield). 1H NMR (400 MHz, DMSO‐d6) δ
ppm: 11.89 (s, 1H, NH‐pyrazole), 9.34 (s, 1H, Ar‐NH‐Ar), 7.41–7.08
(m, 5H, Ph‐H), 6.14 (s, 2H, pyrazole‐H, and pyrimidine‐H), 4.39 (s, 1H,
Ph‐CH2‐Ar), 4.00 (s, 1H, Ph‐CH2‐Ar), 3.72 (s, 2H, diazepane‐H), 3.51
(d, J = 2.7 Hz, 1H, diazepane‐H), 3.19–2.98 (m, 5H, diazepane‐H), 2.75
(s, 3H, CH3‐N), 2.20 (s, 3H, CH3). HRMS calcd. for C21H28N7, [M+H]+,
378.2406; found 378.2403.
2‐(4‐Aminopiperidin‐1‐yl)‐6‐benzyl‐N‐(5‐methyl‐1H‐pyrazol‐3‐yl)‐
pyrimidin‐4‐amine (B4)
Compound B4 was prepared in a similar manner as compound A1, 19b
instead of 17a. Light yellow solid (0.02 g, 76.2% yield). 1H NMR
(400 MHz, DMSO‐d6) δ ppm: 9.22 (s, 1H, Ar‐NH‐Ar), 7.29–7.19 (m, 5H,
Ph‐H), 6.12 (s, 1H, pyrazole‐H), 6.08 (s, 1H, pyrimidine‐H), 4.57–4.54
(m, 2H, Ph‐CH2‐Ar), 3.69 (s, 2H, piperidine‐H), 2.92–2.86 (m, 2H,
piperidine‐H), 2.18 (s, 3H, CH3), 1.84–1.78 (m, 2H, piperidine‐H),
1.23–1.21 (m, 3H, piperidine‐H). HRMS calcd. for C20H26N7, [M+H]+,
364.2250; found 364.2245.
{4‐{4‐Benzyl‐6‐[(5‐methyl‐1H‐pyrazol‐3‐yl)amino]pyrimidin‐2‐yl}‐
piperazin‐1‐yl}(1H‐pyrrol‐2‐yl)methanone (B9)
Light yellow solid (0.03 g, 76.4% yield). 1H NMR (400 MHz, DMSO‐
d6) δ ppm: 12.36 (s, 1H, NH‐pyrazole), 11.53 (s, 1H, NH‐pyrrole),
10.96 (s, 1H, Ar‐NH‐Ar), 7.51–7.19 (m, 5H, Ph‐H), 6.93 (td, J = 2.7,
1.3 Hz, 1H, pyrrole‐H), 6.69–6.55 (m, 1H, pyrrole‐H), 6.38 (s, 1H,
pyrrole‐H), 6.26–6.12 (m, 1H, pyrazole‐H), 6.05 (s, 1H, pyrimidine‐H),
4.40–4.26 (s, 2H, Ph‐CH2‐Ar), 4.26–3.85 (m, 8H, piperazine‐H), 2.24
(s, 3H, CH3). HRMS calcd. for C24H27N8O, [M+H]+, 443.2308; found
443.2308.
6‐Benzyl‐N‐(5‐methyl‐1H‐pyrazol‐3‐yl)‐2‐[4‐(methylamino)
piperidin‐1‐yl]pyrimidin‐4‐amine (B5)
Compound B5 was prepared in a similar manner as compound A1,
19c instead of 17a. Light yellow solid (0.03 g, 79.4% yield). 1H NMR
(400 MHz, DMSO‐d6) δ ppm: 12.83 (brs, 1H, NH‐pyrazole), 11.00 (s,
1H, Ar‐NH‐Ar), 7.39–7.30 (m, 5H, Ph‐H), 6.32 (s, 1H, pyrazole‐H),
6.04 (s, 1H, pyrimidine‐H), 4.74 (d, J = 12.4 Hz, 2H, Ph‐CH2‐Ar), 4.32
(s, 2H, piperidine‐H), 3.32–3.30 (m, 1H, piperidine‐H), 3.22
(t, J = 12.4 Hz, 2H, piperidine‐H), 2.54–2.52 (m, 2H, piperidine‐H),
2.24–2.20 (m, 6H, 2 × CH3), 1.69 (dd, J = 12.4 Hz, 8.1 Hz, 2H,
piperidine‐H). HRMS calcd. for C21H28N7, [M+H]+, 378.2406; found
378.2402.
{4‐{4‐Benzyl‐6‐[(5‐methyl‐1H‐pyrazol‐3‐yl)amino]pyrimidin‐2‐yl}‐
piperazin‐1‐yl}(furan‐2‐yl)methanone (B10)
Light yellow solid (0.04 g, 85.1% yield). 1H NMR (400 MHz, DMSO‐
d6) δ ppm: 11.84 (s, 1H, NH‐pyrazole), 9.31 (s, 1H, Ar‐NH‐Ar), 7.86 (d,
J = 1.7 Hz, 1H, furan‐H), 7.37–7.13 (m, 5H, Ph‐H), 7.04 (d, J = 3.4 Hz,
1H, furan‐H), 6.64 (dd, J = 3.5, 1.8 Hz, 1H, furan‐H), 6.21 (s, 1H,
pyrazole‐H), 6.14 (s, 1H, pyrimidine‐H), 3.91–3.82 (s, 2H, Ph‐CH2‐Ar),
3.91–3.63 (m, 8H, piperazine‐H), 2.19 (s, 3H, CH3). HRMS calcd. for
C
24H26N7O2, [M+H]+, 444.2148; found 444.2147.
6‐Benzyl‐N4‐(5‐methyl‐1H‐pyrazol‐3‐yl)‐N2‐(piperidin‐4‐yl)‐
pyrimidine‐2,4‐diamine (B6)
N2,6‐Dibenzyl‐N4‐(5‐methyl‐1H‐pyrazol‐3‐yl)pyrimidine‐2,4‐
diamine (B11)
Compound B6 was prepared in a similar manner as compound A1, 20
instead of 17a. Light yellow solid (0.03 g, 95.3% yield). 1H NMR
(400 MHz, DMSO‐d6) δ ppm: 11.20 (s, 1H, NH‐pyrazole), 8.72 (s, 1H,
Ar‐NH‐Ar), 7.47–7.24 (m, 5H, Ph‐H), 6.41 (s, 1H, pyrazole‐H),
6.19–5.83 (m, 1H, pyrimidine‐H), 4.00 (s, 2H, Ph‐CH2‐Ar), 3.29 (d,
J = 12.3 Hz, 2H, piperidine‐H), 3.16–2.91 (m, 3H, piperidine‐H), 2.27
(s, 3H, CH3), 2.15 (d, J = 12.3 Hz, 2H, piperidine‐H), 1.90–1.73 (m, 2H,
Light yellow solid (0.03 g, 81.2% yield). 1H NMR (400 MHz, DMSO‐
d6) δ ppm: 11.74 (s, 1H, NH‐pyrazole), 9.16 (s, 1H, Ar‐NH‐Ar),
7.43–7.02 (m, 10H, 2 × Ph‐H), 6.08 (s, 2H, pyrazole‐H, and
pyrimidine‐H), 4.47 (d, J = 6.2 Hz, 2H, Ph‐CH2‐N), 3.67 (s, 2H, Ph‐
CH2‐Ar), 2.12 (s, 3H, CH3). HRMS calcd. for C22H23N6, [M+H]+,
371.1984; found 371.1977.