Sodium Bicarbonate → HCID 86713561, compound

HRID 524030Notes

Reaction equation

HRID 524030 reaction equation
[N+:1]([C:4]1[CH:9]=[CH:8][CH:7]=[C:6]([CH3:10])[C:5]=1[NH:11][C:12]1[N:13]=[CH:14][C:15]2[CH:21]=[C:20]([C:22]3[C:27]([Cl:28])=[C:26]([O:29][CH3:30])[CH:25]=[C:24]([O:31][CH3:32])[C:23]=3[Cl:33])[C:19](=[O:34])[N:18]([CH3:35])[C:16]=2[N:17]=1)([O-])=O.O.[Sn](Cl)Cl.C(=O)(O)[O-].[Na+]>CCOC(C)=O.O>[NH2:1][C:4]1[CH:9]=[CH:8][CH:7]=[C:6]([CH3:10])[C:5]=1[NH:11][C:12]1[N:13]=[CH:14][C:15]2[CH:21]=[C:20]([C:22]3[C:23]([Cl:33])=[C:24]([O:31][CH3:32])[CH:25]=[C:26]([O:29][CH3:30])[C:27]=3[Cl:28])[C:19](=[O:34])[N:18]([CH3:35])[C:16]=2[N:17]=1

Participants

6

Reactant 3

HCID 516892Sodium BicarbonateHCID 43835034Tin dichloride dihydrateHCID 86713563HCID 86713563, compound

Product 1

HCID 86713561HCID 86713561, compoundYield 83.8%

Reagents, catalysts & solvents 2

HCID 962WaterSolventHCID 8857Ethyl AcetateSolvent

Conditions

Temperature
60 °C

Procedure

A mixture of 2-(2-nitro-6-methylphenylamino)-6-(2,6-dichloro-3,5-dimethoxyphenyl)-8-methylpyrido[2,3-d]pyrimidin-7(8H)-one (10) (810 mg, 1.57 mmol) and tin(II) chloride hydrate (1.77 g, 7.86 mmol) in EtOAc (50 mL) was stirred at 60° C. for 2 hours. The reaction was monitored by LCMS. The reaction mixture was basified with saturated aqueous sodium bicarbonate to pH=8-9, diluted with H2O (100 mL), and then extracted with EtOAc (3×100 mL). The combined organic layers were washed with brine (150 mL), dried over sodium sulfate, filtered, and concentrated. The residue was recrystallized with dichloromethane/ethyl acetate/petroleum ether (DCM/EtOAc/PE)=1/1/2 to give 2-(2-amino-6-methylphenylamino)-6-(2,6-dichloro-3,5-dimethoxyphenyl)-8-methylpyrido[2,3-d]pyrimidin-7(8H)-one (11) (640 mg, 83% yield) as a grey solid. (MS (ES+) C23H21Cl2N5O3 requires: 485, 487. found: 486, 488 [M+H]+; 1H-NMR (500 MHz, CDCl3) δ ppm 8.54 (s, 1H), 7.45 (s, 1H), 7.08 (t, J=7.5 Hz, 1H), 6.71 (dd, J=3.5, 7.5 Hz, 2H), 6.65 (br s, 1H), 6.62 (s, 1H), 3.94 (s, 6H), 3.88 (br s, 2H), 3.62 (br s, 3H), 2.24 (s, 3H).

Workup

  1. extractionextracted with EtOAc (3×100 mL)
  2. washThe combined organic layers were washed with brine (150 mL)
  3. dry with materialdried over sodium sulfate
  4. filtrationfiltered
  5. concentrationconcentrated
  6. customThe residue was recrystallized with dichloromethane/ethyl acetate/petroleum ether (DCM/EtOAc/PE)=1/1/2

Sources & evidence

ORD record
ord-fb76c79fdfbb4e799fb4c0997f8ae060
Source dataset
uspto-grants-2016_05
Patent number
US09340514B2

Reaction notes

Loading…