Benzyl Bromide → HCID 20142724, compound

HRID 649195Notes

Reaction equation

HRID 649195 reaction equation
C(NC(C)C)(C)C.C([Li])CCC.[Br:13][C:14]1[CH:15]=[C:16]2[C:21](=[CH:22][CH:23]=1)[C:20](=[O:24])[CH2:19][CH2:18][CH2:17]2.[CH2:25](Br)[C:26]1[CH:31]=[CH:30][CH:29]=[CH:28][CH:27]=1>O1CCCC1>[CH2:25]([CH:19]1[CH2:18][CH2:17][C:16]2[C:21](=[CH:22][CH:23]=[C:14]([Br:13])[CH:15]=2)[C:20]1=[O:24])[C:26]1[CH:31]=[CH:30][CH:29]=[CH:28][CH:27]=1

Participants

6

Reactant 4

HCID 7498Benzyl BromideHCID 7912DiisopropylamineHCID 101050696-Bromo-1-tetraloneHCID 178418339Butyllithium

Product 1

HCID 20142724HCID 20142724, compound

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent2×

Conditions

Temperature
-78 °C

Procedure

Under dry N2, diisopropylamine (1.7 ml, 0.012 mol) was dissolved in tetrahydrofuran (20 ml) and cooled to -78° C. Butyl lithium (6.88 ml of 1.6 M in hexane, 0.011 mol) was added, and the mixture stirred at -20° C for 0.5 hour and then recooled to -78° C. 6-Bromo-3,4-dihydro-1(2H)-naphthalenone (2.25 g, 0.010 mol; J. Am. Chem. Soc. v. 102, p. 7920, 1980), dissolved in tetrahydrofuran (10 ml) was added, the mixture warmed to -20° C. over 0.5 hour and stirred at that temperature for 15 minutes. Finally benzyl bromide (1.3 ml, 0.011 mol) was added, the mixture warmed over 1 hour to ambient temperature, and stirred at that temperature for 16 hours. The reaction was quenched with two volumes of 10% HCl and extracted with 150 ml ether. The organic layer was washed with 100 ml saturated brine, dried (MgSO4), stripped in vacuo, and the residue chromatographed on silica gel using 1:1 hexane:CH2Cl2 as eluant, monitoring by tlc (1:2 hexane:CH2CL2). Recovered was 380 mg of bis-benzylated product (Rf 0.58), 750 mg of title product (Rf 0.50) and 1.1 g of starting material (Rf 0.28), suitable for recycling.

Workup

  1. customrecooled to -78° C
  2. additionwas added
  3. temperaturethe mixture warmed to -20° C. over 0.5 hour
  4. stirringstirred at that temperature for 15 minutes
  5. temperaturethe mixture warmed over 1 hour to ambient temperature
  6. stirringstirred at that temperature for 16 hours
  7. customThe reaction was quenched with two volumes of 10% HCl
  8. extractionextracted with 150 ml ether
  9. washThe organic layer was washed with 100 ml saturated brine
  10. dry with materialdried (MgSO4)
  11. customthe residue chromatographed on silica gel using 1:1 hexane
  12. customRecovered

Sources & evidence

ORD record
ord-8c597e970a214656960386c6d7522ff5
Source dataset
uspto-grants-1988_04
Patent number
US04738972

Reaction notes

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