4-Bromoanisole → 5-Ethyl-2,4'-dimethoxybiphenyl

HRID 344924Notes

Reaction equation

HRID 344924 reaction equation
[Mg].Br[C:3]1[CH:8]=[C:7]([CH2:9][CH3:10])[CH:6]=[CH:5][C:4]=1[O:11][CH3:12].Br[C:14]1[CH:19]=[CH:18][C:17]([O:20][CH3:21])=[CH:16][CH:15]=1.ClCl.O.[Cl-].[NH4+]>O1CCCC1.[Ni](Cl)Cl>[CH2:9]([C:7]1[CH:6]=[CH:5][C:4]([O:11][CH3:12])=[C:3]([C:14]2[CH:19]=[CH:18][C:17]([O:20][CH3:21])=[CH:16][CH:15]=2)[CH:8]=1)[CH3:10]

Participants

8

Reactant 5

HCID 77304-BromoanisoleHCID 24526ChlorineHCID 5462224MagnesiumHCID 138388252-Bromo-4-ethyl-1-methoxybenzene2×HCID 57429219Ammonium chloride monohydrate

Product 1

HCID 541842175-Ethyl-2,4'-dimethoxybiphenyl

Reagents, catalysts & solvents 2

HCID 24385Nickel DichlorideCatalystHCID 8028TetrahydrofuranSolvent3×

Procedure

A mixture was prepared by suspending 7.2 g of metallic magnesium into 40 ml of tetrahydrofuran (THF). The mixture, wherein 1 ml of 2-bromo-4-ethylanisole was added, was stirred at room temperature. After an exothermic reaction occurred, the reaction mixture was diluted with 100 ml of THF, followed by dropwise addition of the solution which was prepared by dissolving 63.5 g of 2-bromo-4-ethylanisole into 160 ml of THF. The addition was took 2 hours. The reaction mixture was stirred for 1 hour, reflexed by heating for further 1 hour and cooled down to 0° C. in internal temperature, wherein 59 g of p-bromoanisole was added thereinto, 0.5 g power of the complex compound of nickel chloride and 1,3-diphenylphosphynopropane (Nidppp Cl2) was added in the reaction mixture, and stirred overnight. The reactant was transferred into ammonium chloride water solution and extracted with diethylether. The extract was washed with an aqueous solution saturated with NaCl, dried with sodium sulfate and concentrated. The concentrate was distilled under reduced pressure to yield 51.6 g of 5-ethyl-2,4'-dimethoxy-biphenyl having a b.p. of 135°-148° C. (0.5 mmHg).

Workup

  1. customA mixture was prepared
  2. customAfter an exothermic reaction
  3. additionfollowed by dropwise addition of the solution which
  4. customwas prepared
  5. additionThe addition
  6. stirringThe reaction mixture was stirred for 1 hour
  7. temperatureby heating for further 1 hour
  8. additionwas added
  9. stirringstirred overnight
  10. extractionextracted with diethylether
  11. washThe extract was washed with an aqueous solution saturated with NaCl
  12. dry with materialdried with sodium sulfate
  13. concentrationconcentrated
  14. distillationThe concentrate was distilled under reduced pressure

Sources & evidence

ORD record
ord-eb544e38ca964e91b097a82135e1ebc8
Source dataset
uspto-grants-1991_10
Patent number
US05053548

Reaction notes

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