Hydrochloric Acid → 4-bromo-1-chloro-2-cyclopropoxybenzene

HRID 1094437Notes

Reaction equation

HRID 1094437 reaction equation
[Br:1][C:2]1[CH:3]=[CH:4][C:5]([Cl:9])=[C:6]([OH:8])[CH:7]=1.Br[CH:11]1[CH2:13][CH2:12]1.C(=O)([O-])[O-].[Cs+].[Cs+].Cl>CN(C)C(=O)C>[Br:1][C:2]1[CH:3]=[CH:4][C:5]([Cl:9])=[C:6]([O:8][CH:11]2[CH2:13][CH2:12]2)[CH:7]=1

Participants

6

Reactant 4

HCID 313Hydrochloric AcidHCID 10796Cesium carbonateHCID 78037Bromocyclopropane2×HCID 8203925-Bromo-2-chlorophenol

Product 1

HCID 580075714-bromo-1-chloro-2-cyclopropoxybenzeneYield 87.9%

Reagents, catalysts & solvents 1

HCID 31374DimethylacetamideSolvent

Conditions

Temperature
150 °C

Procedure

A mixture of 5-bromo-2-chlorophenol (543 mg, 2.62 mmol), bromocyclopropane (836 μl, 10.47 mmol) and caesium carbonate (1.701 g, 5.24 mmol) in N,N-dimethylacetamide (7.5 ml) was stirred for 47 h at 150° C. After 25.25 h further bromocyclopropane (836 μl, 10.47 mmol) was added. The reaction mixture was poured onto ice-water (40 ml) and set to pH=2 with aqueous HCl (1 N, 9.5 ml). This mixture was extracted with TBME (twice 50 ml). The organic layers were washed with brine (40 ml), combined and dried over sodium sulfate. Concentration and purification by chromatography (SiO2, heptane:ethyl acetate=100:0 to 67:33) afforded the title compound (570 mg, 87%) as a light yellow oil. MS m/e: 248.0 [M+H]+

Workup

  1. additionThe reaction mixture was poured onto ice-water (40 ml)
  2. extractionThis mixture was extracted with TBME (twice 50 ml)
  3. washThe organic layers were washed with brine (40 ml)
  4. dry with materialdried over sodium sulfate
  5. concentrationConcentration and purification by chromatography (SiO2, heptane:ethyl acetate=100:0 to 67:33)

Sources & evidence

ORD record
ord-83ad345e71244ee79b5029d97b6f22a0
Source dataset
uspto-grants-2012_03
Patent number
US08133909B2

Reaction notes

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