Stannous Chloride → 1-(2,5-Diaminopyrimidin-4-yl)indazole-6-carbonitrile

HRID 1398491Notes

Reaction equation

HRID 1398491 reaction equation
[NH2:1][C:2]1[NH:7][CH:6]([N:8]2[C:16]3[C:11](=[CH:12][CH:13]=[C:14]([C:17]#[N:18])[CH:15]=3)[CH:10]=[N:9]2)[C:5]([N+:19]([O-])=O)=[CH:4][N:3]=1.[Sn](Cl)Cl>C(O)C>[NH2:1][C:2]1[N:7]=[C:6]([N:8]2[C:16]3[C:11](=[CH:12][CH:13]=[C:14]([C:17]#[N:18])[CH:15]=3)[CH:10]=[N:9]2)[C:5]([NH2:19])=[CH:4][N:3]=1

Participants

4

Reactant 2

HCID 24479Stannous ChlorideHCID 178509490HCID 178509490, compound

Product 1

HCID 601639861-(2,5-Diaminopyrimidin-4-yl)indazole-6-carbonitrileYield 11%

Reagents, catalysts & solvents 1

HCID 702EthanolSolvent

Conditions

Temperature
60 °C

Procedure

A mixture of 1-(2-amino-5-nitro-3,4-dihydropyrimidin-4-yl)-1H-indazole-6-carbonitrile (40% purity, 400 mg, 0.64 mmol) and tin (II) chloride (577 mg, 2.56 mmol) in ethanol (15 mL) was heated at 60° C. for 2 hr then at 70° C. for 3 hr. LC-MS (Method B) showed 11% desired product and 74% degradation. The reaction mixture was concentrated in vacuo. The residue was vigorously stirred with a mixture of saturated aqueous Rochelle salt (potassium sodium tartrate (20 mL), saturated aqueous NaHCO3 (20 mL) and EtOAc (30 mL) for 30 min. The EtOAc layer was washed with brine (10 mL), dried over Na2SO4, filtered and concentrated in vacuo. The crude was purified by column chromatography (Biotage) (100% EtOAc) to give the title compound as a pale yellow solid: 1H NMR (250 MHz, DMSO) δ 5.40 (2H, br. s.), 6.30 (2H, s), 7.69 (1H, dd, J=8.38, 1.22 Hz), 8.01-8.25 (2H, m), 8.62 (1H, d, J=0.76 Hz), 9.31 (1H, s); LC-MS: m/z=+252.0 (M+H)+.

Sources & evidence

ORD record
ord-75f998548000435289e3e9e8444d9cee
Source dataset
uspto-grants-2014_12
Patent number
US08901313B2

Reaction notes

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