Stannous chloride dihydrate → 4-N-(2-amino-5-bromophenyl)pyrimidine-2,4-diamine

HRID 1398503Notes

Reaction equation

HRID 1398503 reaction equation
[Br:1][C:2]1[CH:3]=[CH:4][C:5]([N+:16]([O-])=O)=[C:6]([NH:8][C:9]2[CH:14]=[CH:13][N:12]=[C:11]([NH2:15])[N:10]=2)[CH:7]=1.O.O.[Sn](Cl)Cl>C(O)C>[NH2:16][C:5]1[CH:4]=[CH:3][C:2]([Br:1])=[CH:7][C:6]=1[NH:8][C:9]1[CH:14]=[CH:13][N:12]=[C:11]([NH2:15])[N:10]=1

Participants

4

Reactant 2

HCID 61436Stannous chloride dihydrateHCID 681819124-N-(5-bromo-2-nitrophenyl)pyrimidine-2,4-diamine

Product 1

HCID 681818104-N-(2-amino-5-bromophenyl)pyrimidine-2,4-diamine

Reagents, catalysts & solvents 1

HCID 702EthanolSolvent

Conditions

Temperature
65 °C

Procedure

To a solution of 4-N-(5-bromo-2-nitrophenyl)pyrimidine-2,4-diamine (5.06 g, 16.32 mmol) in ethanol (110 mL) was added tin(II) chloride dihydrate (12.89 g, 57.11 mmol). The reaction mixture was stirred at 65° C. for 2 hr. The reaction mixture was evaporated to dryness and ice-water added. The pH of the mixture was adjusted to 10 using saturated aqueous Na2CO3 solution. EtOAc was added followed by saturated aqueous Rochelles salt (potassium sodium tartrate). The resulting mixture was stirred until separate layers were observed. The organic layer was extracted and the extraction repeated (2×) with EtOAc and DCM. Combined organic layer were washed with brine, dried over Na2SO4, filtered and concentrated in vacuo to give the title compound as a pale yellow solid: 1H NMR (250 MHz, DMSO) δ 5.05 (2H, br. s), 5.79 (1H, d, J=5.79 Hz), 6.08 (2H, br. s), 6.68 (1H, d, J=8.53 Hz), 7.02 (1H, dd, J=8.60, 2.36 Hz), 7.36 (1H, d, J=2.28 Hz), 7.75 (1H, d, J=5.63 Hz), 8.15 (1H, s); LC-MS: m/z=+279.9, 281.9 (M+H)+.

Workup

  1. customThe reaction mixture was evaporated to dryness and ice-water
  2. additionadded
  3. additionEtOAc was added
  4. stirringThe resulting mixture was stirred
  5. customuntil separate layers
  6. extractionThe organic layer was extracted
  7. extractionthe extraction
  8. washCombined organic layer were washed with brine
  9. dry with materialdried over Na2SO4
  10. filtrationfiltered
  11. concentrationconcentrated in vacuo

Sources & evidence

ORD record
ord-8fc6cfd792eb47a19f25c5a802ce3007
Source dataset
uspto-grants-2014_12
Patent number
US08901313B2

Reaction notes

Loading…