tert-Butanol → tert-Butyl (1-(4-bromophenyl)cyclopropyl)carbamate

HRID 51768Notes

Reaction equation

HRID 51768 reaction equation
[Br:1][C:2]1[CH:7]=[CH:6][C:5]([C:8]2(C(O)=O)[CH2:10][CH2:9]2)=[CH:4][CH:3]=1.C1(P(N=[N+]=[N-])(C2C=CC=CC=2)=[O:21])C=CC=CC=1.C([N:33]([CH2:36]C)CC)C.[C:38]([OH:42])([CH3:41])([CH3:40])[CH3:39]>>[Br:1][C:2]1[CH:3]=[CH:4][C:5]([C:8]2([NH:33][C:36](=[O:21])[O:42][C:38]([CH3:41])([CH3:40])[CH3:39])[CH2:9][CH2:10]2)=[CH:6][CH:7]=1

Participants

5

Reactant 4

HCID 6386tert-ButanolHCID 8471TriethylamineHCID 199401P,P-Diphenylphosphinic azideHCID 162279661-(4-Bromophenyl)cyclopropane-1-carboxylic acid2×

Product 1

HCID 53216208tert-Butyl (1-(4-bromophenyl)cyclopropyl)carbamateYield 67%

Procedure

A solution of 1-(4-bromophenyl)-cyclopropanecarboxylic acid (Intermediate 114, 2.32 g, 9.62 mmols), diphenylphosphoryl azide (2.65 g, 9.62 mmols), triethylamine (973.0 mg, 9.62 mmols) in 40 mL tert-BuOH (distilled from Na°) was heated to reflux for 17 h. The solution was concentrated under reduced pressure and the residue dissolved in EtOAc and washed with 5% aqueous HCl, H2O, saturated aqueous NaHCO3, and saturated aqueous NaCl before being dried over MgSO4. Concentration of the dry solution under reduced pressure and column chromatography (5-10% EtOAc-hexanes) afforded 2.01 g (67%) of the title compound as a colorless solid.

Workup

  1. temperatureto reflux for 17 h
  2. concentrationThe solution was concentrated under reduced pressure
  3. dissolutionthe residue dissolved in EtOAc
  4. washwashed with 5% aqueous HCl, H2O, saturated aqueous NaHCO3, and saturated aqueous NaCl
  5. dry with materialbefore being dried over MgSO4

Sources & evidence

ORD record
ord-894a6e4f5ecf46918a6a23de677c4a9d
Source dataset
uspto-grants-2004_03
Patent number
US06713647B2

Reaction notes

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