Nitrogen → HCID 67292943, compound

HRID 1877702Notes

Reaction equation

HRID 1877702 reaction equation
O1[CH:5]=[CH:4][C:3]([C:6]2([NH:9][C:10](=[O:16])[O:11][C:12]([CH3:15])([CH3:14])[CH3:13])[CH2:8][CH2:7]2)=[CH:2]1.[N:17]#[N:18].C([O-])(O)=O.[Na+].BrN1C(=O)CCC1=O>CC(C)=O.C1COCC1.O>[N:17]1[CH:5]=[CH:4][C:3]([C:6]2([NH:9][C:10](=[O:16])[O:11][C:12]([CH3:15])([CH3:14])[CH3:13])[CH2:8][CH2:7]2)=[CH:2][N:18]=1

Participants

8

Reactant 4

HCID 947NitrogenHCID 67184N-bromobutanimideHCID 516892Sodium BicarbonateHCID 67292253HCID 67292253, compound

Product 1

HCID 67292943HCID 67292943, compound

Reagents, catalysts & solvents 3

HCID 180AcetoneSolventHCID 962WaterSolventHCID 8028TetrahydrofuranSolvent

Conditions

Temperature
-20 °C

Procedure

A solution of tert-butyl 1-(furan-3-yl)cyclopropylcarbamate (2.15 g, 9.64 mmol, 1.0 eq), in acetone (86 ml) and water (86 ml) at r.t. was purged with N2 and cooled to −20° C. NaHCO3 (1.62 g, 19.28 mmol, 2.0 eq) and N-bromosuccinimide (2.23 g, 12.52 mmol, 1.3 eq) were added to the mixture at −20° C. and the stirring was continued at the same temperature for 2 hr. To the reaction mixture at −20° C. was added THF (4.3 ml) and the temperature raised to 0° C. over 30 min. Acetone was removed from the reaction mixture with a stream of N2, and to the residue at 0° C. was added isopropanol (86 ml) followed by hydrazine hydrate (12.9 ml). The reaction mixture was stirred at r.t. overnight. Product formation was confirmed by LCMS. The solvent was evaporated under reduced pressure, and the residue diluted with water and then extracted with EtOAC. The organic was washed with brine, dried over Na2SO4 and concentrated. The crude product was purified by silica gel (60-120) column chromatography using 4% MeOH/CHCl3 as an eluent. Yield: 1.3 g (57.5%). 1H NMR (400 MHz, CDCl3): δ 9.04 (d, J=5.6, 1H), 8.95 (d, J=2.8, 1H), 7.19 (s, 1H), 5.25 (bs, 1H), 1.42 (s, 9H), 1.25 (bs, 4H). LCMS: (ES+) m/z=236.2 (M+H)+

Workup

  1. temperaturethe temperature raised to 0° C. over 30 min
  2. customAcetone was removed from the reaction mixture with a stream of N2
  3. additionto the residue at 0° C. was added isopropanol (86 ml)
  4. customThe solvent was evaporated under reduced pressure
  5. additionthe residue diluted with water
  6. extractionextracted with EtOAC
  7. washThe organic was washed with brine
  8. dry with materialdried over Na2SO4
  9. concentrationconcentrated
  10. customThe crude product was purified by silica gel (60-120) column chromatography

Sources & evidence

ORD record
ord-36a47b0f71444a5bb24f8d3d4a547bce
Source dataset
uspto-grants-2012_11
Patent number
US08309558B2

Reaction notes

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