Water → 4-Bromo-2-(2-chloro-1,1-dimethylethyl)anisole

HRID 1790212Notes

Reaction equation

HRID 1790212 reaction equation
S(=O)(=O)(O)O.[Br:6][C:7]1[CH:12]=[CH:11][C:10]([O:13][CH3:14])=[CH:9][CH:8]=1.O.[Cl:16][CH2:17][C:18]([CH3:20])=[CH2:19]>ClCCl>[Br:6][C:7]1[CH:12]=[CH:11][C:10]([O:13][CH3:14])=[C:9]([C:18]([CH3:20])([CH3:19])[CH2:17][Cl:16])[CH:8]=1

Participants

6

Reactant 4

HCID 962WaterHCID 1118Sulfuric AcidHCID 77304-BromoanisoleHCID 112413-Chloro-2-methyl-1-propene

Product 1

HCID 46057784-Bromo-2-(2-chloro-1,1-dimethylethyl)anisole

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent

Procedure

Sulfuric acid (2 mL, 0.033 mol) was added dropwise under argon to 4-bromoanisole (14.6 mL, 0.117 mol). The mixture was warmed to 40–43° C. (warm water bath) and 3-chloro-2-methyl propene was added dropwise in 4 equal portions over 2 hrs. After 2 hrs at 40–43° C. the solution was diluted with dichloromethane and washed successively with water, saturated aqueous NaHCO3, water and brine, dried (Mg2SO4), filtered and evaporated. The residue was crystallized from hexanes to give 14.1 g of 4-bromo-2-(2-chloro-1,1-dimethyl-ethyl)-1-methoxy-benzene. The mother liquor was further purified on silica gel (10% ethyl acetate in hexane) to afford additional 4.8 g of product. 58% yield. 1H NMR (300 MHz; CDCl3): δ 1.43 (s, 6 H), 3.82 (s, 3 H), 3.93 (s, 2 H), 6.75 (dd, J=2.4 Hz and 7.2 Hz, 1 H), 7.32 (m, 2 H).

Workup

  1. temperatureThe mixture was warmed to 40–43° C.
  2. additionwas added dropwise in 4 equal portions over 2 hrs
  3. washwashed successively with water, saturated aqueous NaHCO3, water and brine
  4. dry with materialdried (Mg2SO4)
  5. filtrationfiltered
  6. customevaporated
  7. customThe residue was crystallized from hexanes

Sources & evidence

ORD record
ord-6143f107a610417eb57f1701b3304807
Source dataset
uspto-grants-2006_07
Patent number
US07071218B2

Reaction notes

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