Hydrochloric Acid → 2-Chloro-5-Tert-Butyl-1,3-Dimethylbenzene

HRID 922090Notes

Reaction equation

HRID 922090 reaction equation
Br[C:2]1[C:7]([CH3:8])=[CH:6][C:5]([C:9]([CH3:12])([CH3:11])[CH3:10])=[CH:4][C:3]=1[CH3:13].O.[ClH:15]>CN(C)C=O.Cl[Ni]Cl>[Cl:15][C:2]1[C:7]([CH3:8])=[CH:6][C:5]([C:9]([CH3:12])([CH3:11])[CH3:10])=[CH:4][C:3]=1[CH3:13]

Participants

6

Reactant 3

HCID 313Hydrochloric AcidHCID 962WaterHCID 2203642-Bromo-5-tert-butyl-1,3-dimethylbenzene

Product 1

HCID 600078972-Chloro-5-Tert-Butyl-1,3-Dimethylbenzene

Reagents, catalysts & solvents 2

HCID 24385Nickel DichlorideCatalystHCID 6228DimethylformamideSolvent2×

Procedure

In a 500 mL round bottom flask 4.50 g of 2-bromo-5-tert-butyl-1,3-dimethylbenzene (18.6 mmol) and 9.50 g of NiCl2.6 H2O (40.0 mmol) were added. Then 30 mL of N,N-dimethylformamide was added to the flask, giving a blue-green solution. The flask was fitted with a condenser and was left to reflux with stirring. After 0.5 hours the solution was dark blue. After refluxing for 5 days the mixture was cooled to rt and then diluted with 25 mL of 2 M HCl. The aqueous phase was extracted with 40 mL of ethyl acetate. The volatiles were removed from the extract by evaporation to give a white solid. (91% conversion to the title product) All of the solids were dissolved in 25 mL of N,N-dimethylformamide and the solution was placed in a 125 mL round bottom flask. Then 5.1 g of NiCl2·6 H2O (21.5 mmol) was added to the flask. The flask was fitted with a condenser and was left to reflux with stirring. After 0.5 hours the solution was dark blue. After refluxing for 5 days the mixture was cooled to rt and then diluted with 25 mL of 2 M HCl. The aqueous phase was extracted with 40 mL of ethyl acetate. The volatiles were removed from the extract by evaporation to give a white solid. C12H17Cl, fw=196.72. Yield 3.51 g, 95.6%. Mp: 39° C. (melt). 1H NMR (300 MHz, CDCl3): δ 7.01 (s, 2H), 2.30 (s, 6H), 1.22 (s, 9H). Rf=0.69 (cyclohexane/silica).

Workup

  1. customgiving a blue-green solution
  2. customThe flask was fitted with a condenser
  3. waitwas left
  4. temperatureto reflux
  5. temperatureAfter refluxing for 5 days the mixture
  6. extractionThe aqueous phase was extracted with 40 mL of ethyl acetate
  7. customThe volatiles were removed from the
  8. extractionextract by evaporation
  9. customto give a white solid

Sources & evidence

ORD record
ord-ab69726d7000469d89397a3088e5ccc3
Source dataset
uspto-grants-2016_03
Patent number
US09278894B2

Reaction notes

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