4-Bromobiphenyl → HCID 13392401, compound

HRID 1980513Notes

Reaction equation

HRID 1980513 reaction equation
Br[C:2]1[CH:7]=[CH:6][C:5]([C:8]2[CH:13]=[CH:12][CH:11]=[CH:10][CH:9]=2)=[CH:4][CH:3]=1.[Mg].[Cl:15][CH2:16][SiH2:17][CH:18](Cl)Cl.[CH2:21](N(CC)CC)C.[O:28]1[CH2:32][CH2:31]CC1>C(O)(C)C>[C:5]1([C:8]2[CH:13]=[CH:12][CH:11]=[CH:10][CH:9]=2)[CH:6]=[CH:7][C:2]([Si:17]([CH2:16][Cl:15])([CH3:18])[O:28][CH:32]([CH3:31])[CH3:21])=[CH:3][CH:4]=1

Participants

7

Reactant 5

HCID 71014-BromobiphenylHCID 8028Tetrahydrofuran4×HCID 8471TriethylamineHCID 5462224MagnesiumHCID 57370169HCID 57370169, compound

Product 1

HCID 13392401HCID 13392401, compoundYield 96%

Reagents, catalysts & solvents 1

HCID 3776IsopropanolSolvent

Procedure

A solution of 73.3 g (0.315 mol) of 4-bromobiphenyl in 300 ml of tetrahydrofuran was added dropwise to a stirred suspension of 7.64 g (0.315 mol) of magnesium in 100 ml of tetrahydrofuran at a rate that maintained gentle reflux. The resulting clear solution was stirred at room temperature for 1 hour and then cooled in ice, and a solution of 40 ml (0.315 mol) of chloromethyl(dichloro)methylsilane in 100 ml of tetrahydrofuran was added rapidly. The resulting solution was stirred at room temperature for 20 hours, treated with 50 ml of isopropanol, and cooled in ice again. A solution of 48 ml (0.344 mol) of triethylamine in tetrahydrofuran was then added at a rate that held the mixture below 25°. Stirring at room temperature for 90 minutes gave a slurry. Filtration, evaporation of the filtrate, trituration with hexanes, and a second filtration removed residual amine hydrochloride. Evaporation of the hexanes solution gave 92 g (96%) of the title compound as a pale yellow oil that solidified on standing: m.p. 35°-38°; nmr (CDCl3) 0.5 (3H, s), 1.2 (6H, d), 3.0 (2H, s), 4.2 (1H, septet), 7.3-7.8 (9H, m).

Workup

  1. temperaturemaintained gentle reflux
  2. temperaturecooled in ice
  3. stirringThe resulting solution was stirred at room temperature for 20 hours
  4. temperaturecooled in ice again
  5. customthe mixture below 25°
  6. stirringStirring at room temperature for 90 minutes
  7. customgave a slurry
  8. filtrationFiltration, evaporation of the filtrate, trituration with hexanes
  9. filtrationa second filtration
  10. customremoved residual amine hydrochloride
  11. customEvaporation of the hexanes solution

Sources & evidence

ORD record
ord-7c2b613012924208bf933f793108fd55
Source dataset
uspto-grants-1985_04
Patent number
US04510136

Reaction notes

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