Heteropyridopyrimidinone derivatives as cdk inhibitors and their applications
A technology of hetero-substituted pyridine and pyrimidinone, which is applied in the field of drug preparation and can solve problems such as large toxic and side effects
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Embodiment 1
[0043] Compound (I-1) 6,6-Dimethyl-8-isopropyl-2-(5-(1-piperazinyl)-pyridine-2-amino)-6H-pyrimidine[5,4-b] [1,4]oxazin-7(8H)-one
[0044] Step 1: 2,4-dichloro-5-methoxypyrimidine (1.0 g, 5.59 mmol), isopropylamine (0.33 g, 5.59 mmol), N,N-diisopropylethylamine (7.2 g, 55.9 mmol ) into isopropanol (IPA, 10mL), N 2 Under the protection of 100 ℃ reaction 6h. Concentrate the solvent to dryness, add H to the residue 2 O (50mL) / dichloromethane (DCM, 50mL) was stirred and extracted, the organic layer was dried, filtered, and concentrated to give a pale yellow solid 2-chloro-N-isopropyl-5-methoxypyrimidine-4-ammonia (0.78g , crude product yield 69.3%).
[0045] Step 2: 2-Chloro-N-isopropyl-5-methoxypyrimidine-4-ammonia (0.78g, 3.88mmol) was added to DCM (15mL), and BBr was added dropwise under ice bath 3 (14.5g, 58.2mmol) in DCM (15mL), the dropwise addition was completed, warmed up to room temperature and stirred for 10h, then methanol (10mL) was added dropwise to quench the rea...
Embodiment 2
[0050] Compound (I-2) 6,6-Dimethyl-8-cyclopentyl-2-(5-(1-piperazinyl)-pyridine-2-amino)-6H-pyrimidine[5,4-b] [1,4]oxazin-7(8H)-one
[0051] The synthesis of compound I-2 was carried out according to the method in Example 1, and the starting material was 2-chloro-6,6-dimethyl-8-cyclopentyl-6H-pyrimidine[5,4-b][1,4] Oxazin-7(8H)-one (synthesis method is similar to Example 1, starting materials are 2,4-dichloro-5-methoxypyrimidine and cyclopentylamine) and 4-(6-aminopyridine-3 -yl) tert-butyl piperazine-1-carboxylate. The final product 6,6-dimethyl-8-cyclopentyl-2-(5-(1-piperazinyl)-pyridine-2-amino)-6H-pyrimidine[5,4-b][1, 4] Oxazin-7(8H)-one hydrochloride (I-2), pale yellow solid. MS(m / z): 424[M+H] + . 1 H NMR (DMSO-d 6 ): δ: 11.88 (br, 1H), 9.77 (br, 2H), 8.26 (s, 1H), 8.24-8.22 (d, J=8.0Hz, 1H), 7.93 (s, 1H), 7.70-7.68 ( d, J=8.0Hz, 1H), 5.37-5.23(m, 1H), 4.61(m, 4H), 3.45(m, 4H), 2.05-1.55(m, 8H), 1.48(s, 6H).
Embodiment 3
[0053] Compound (I-3) 6,6-Dimethyl-8-cyclopentyl-2-(5-(4-ethyl-1-piperazinyl)methyl-pyridine-2-amino)-6H-pyrimidine [5,4-b][1,4]oxazin-7(8H)-one
[0054] The synthesis of compound I-3 was carried out according to the method in Example 1, and the starting material was 2-chloro-6,6-dimethyl-8-cyclopentyl-6H-pyrimidine[5,4-b][1,4] Oxazin-7(8H)-one and 5-[(4-ethylpiperazin-1-yl)methyl]pyridin-2-amine. The final product 6,6-dimethyl-8-cyclopentyl-2-(5-(4-ethyl-1-piperazinyl)methyl-pyridine-2-amino)-6H-pyrimidine [5, 4-b][1,4]oxazin-7(8H)-one hydrochloride (I-3), white solid. MS(m / z): 466[M+H] + . 1 H NMR (DMSO-d 6 ): δ: 12.04 (br, 1H), 11.83 (br, 1H), 8.53 (s, 1H), 8.36-8.34 (d, J=8.0Hz, 1H), 8.19 (s, 1H), 7.72-7.70 ( d, J=8.0Hz, 1H), 5.29-5.21(m, 1H), 4.41(m, 4H), 3.59-3.51(m, 6H), 3.08(m, 2H), 1.99-1.47(m, 8H) , 1.39 (s, 6H), 1.19-1.15 (t, J=8.0Hz, 3H).
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