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

HRID 72392Notes

Reaction equation

HRID 72392 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.C([N:17]([CH2:21]C)C(C)C)(C)C.C1(P(N=[N+]=[N-])(C2C=CC=CC=2)=[O:30])C=CC=CC=1.[C:40]([OH:44])([CH3:43])([CH3:42])[CH3:41]>C1(C)C=CC=CC=1>[Br:1][C:2]1[CH:3]=[CH:4][C:5]([C:8]2([NH:17][C:21](=[O:30])[O:44][C:40]([CH3:43])([CH3:42])[CH3:41])[CH2:9][CH2:10]2)=[CH:6][CH:7]=1

Participants

6

Reactant 4

HCID 6386tert-ButanolHCID 81531DiisopropylethylamineHCID 199401P,P-Diphenylphosphinic azideHCID 162279661-(4-Bromophenyl)cyclopropane-1-carboxylic acid

Product 1

HCID 53216208tert-Butyl (1-(4-bromophenyl)cyclopropyl)carbamate

Reagents, catalysts & solvents 1

HCID 1140TolueneSolvent

Procedure

To the solution of 1-(4-bromophenyl)cyclopropanecarboxylic acid (40 g, 165 mmol, available from Amatek Chemical #AC-0350) in toluene (800 ml), in the presence of activated molecular sieves (15 g), N,N-diisopropylethylamine (27.5 g, 497 mmol), Diphenylphosphoryl azide (54.7 g, 215 mmol) and tert-Butanol (380 ml) were added. The resulting mixture was refluxed 5 hours. The mixture was cooled to room temperature and the solvents evaporated in vacuo. The residue was dissolved in ethyl acetate (200 ml) and washed with 5% citric acid (200 ml), aqueous NaHCO3 (200 ml) and brine (200 ml). Collected organics after drying over Na2SO4 and solvent evaporation afforded a crude residue which was purified by flash chromatography on silica gel eluting with a mixture petroleum ether/ethyl acetate 4:1. Collected fractions after solvent evaporation afforded the title compound (D4) (23.0 g) as a solid.

Workup

  1. temperatureThe resulting mixture was refluxed 5 hours
  2. customthe solvents evaporated in vacuo
  3. dissolutionThe residue was dissolved in ethyl acetate (200 ml)
  4. washwashed with 5% citric acid (200 ml), aqueous NaHCO3 (200 ml) and brine (200 ml)
  5. dry with materialCollected organics after drying over Na2SO4 and solvent evaporation
  6. customafforded a crude residue which
  7. customwas purified by flash chromatography on silica gel eluting with a mixture petroleum ether/ethyl acetate 4:1
  8. customCollected fractions after solvent evaporation

Sources & evidence

ORD record
ord-00e484cfb6864369835e2c1a80c36aa5
Source dataset
uspto-grants-2014_09
Patent number
US08828987B2

Reaction notes

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