Stannous chloride dihydrate → (1R)-5-Bromo-2,3-dihydro-1H-inden-1-amine

HRID 1913400Notes

Reaction equation

HRID 1913400 reaction equation
[N:1]([C@H:4]1[C:12]2[C:7](=[CH:8][C:9]([Br:13])=[CH:10][CH:11]=2)[CH2:6][CH2:5]1)=[N+]=[N-].O.O.Cl[Sn]Cl>CO>[Br:13][C:9]1[CH:8]=[C:7]2[C:12](=[CH:11][CH:10]=1)[C@H:4]([NH2:1])[CH2:5][CH2:6]2

Participants

4

Reactant 2

HCID 61436Stannous chloride dihydrateHCID 59179602(R)-1-azido-5-bromo-indane

Product 1

HCID 28206722(1R)-5-Bromo-2,3-dihydro-1H-inden-1-amineYield 64%

Reagents, catalysts & solvents 1

HCID 887MethanolSolvent

Procedure

A solution of (R)-1-azido-5-bromo-indane (154 g, 0.645 mol) was dissolved in methanol (2.4 L) and SnCl2.2H2O (265 g, 1.18 mol) was added. The mixture was stirred at room temperature overnight (TLC indicated no starting material) and was concentrated to dryness. The resulting residue was treated with 2N aqueous NaOH (2.5 L) and EtOAc (1.5 L). The mixture was stirred for 1 hour and filtered through Celite® with the aid of EtOAc (3×250 ml). The organic solution was separated and the aqueous layer was extracted with EtOAc (3×2 L). The combined organic extracts were washed with 1 N HCl (2×2 L) followed by water (2 L). The pH of the combined aqueous layers was adjusted to 11 with cold saturated NaOH solution and the mixture was extracted with EtOAc (3×2 L). The combined organic extracts were dried over MgSO4, filtered and concentrated to give (87.5 g, 64.0%) (1R)-5-bromoindan-1-amine as a dark yellow oil which solidified upon refrigeration. MS (ES+) 213.9 (M+H)+. 1H NMR (CDCl3) δ 1.70-1.75 (m, 1H), 2.40-2.45 (m, 1H), 2.77-2.82 (m, 1H), 2.93-2.97 (m, 1H), 4.28-4.33 (m, 1H), 7.18-7.23 (m, 1H), 7.36-7.41 (m, 2H).

Workup

  1. concentrationwas concentrated to dryness
  2. additionThe resulting residue was treated with 2N aqueous NaOH (2.5 L) and EtOAc (1.5 L)
  3. stirringThe mixture was stirred for 1 hour
  4. filtrationfiltered through Celite® with the aid of EtOAc (3×250 ml)
  5. customThe organic solution was separated
  6. extractionthe aqueous layer was extracted with EtOAc (3×2 L)
  7. washThe combined organic extracts were washed with 1 N HCl (2×2 L)
  8. extractionthe mixture was extracted with EtOAc (3×2 L)
  9. dry with materialThe combined organic extracts were dried over MgSO4
  10. filtrationfiltered
  11. concentrationconcentrated

Sources & evidence

ORD record
ord-ae3ed768995f45df8cbdec7dba9e87ba
Source dataset
uspto-grants-2013_12
Patent number
US08609680B2

Reaction notes

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