Benzyl Bromide → Benzene, [(4-pentynyloxy)methyl]-

HRID 1522999Notes

Reaction equation

HRID 1522999 reaction equation
[H-].[Na+].[C:3]([OH:8])#[C:4][CH2:5][CH2:6][CH3:7].[CH:9]1[CH:14]=[CH:13][C:12]([CH2:15]Br)=[CH:11][CH:10]=1>C1COCC1>[CH2:3]([O:8][CH2:15][C:12]1[CH:13]=[CH:14][CH:9]=[CH:10][CH:11]=1)[CH2:4][CH2:5][C:6]#[CH:7]

Participants

5

Reactant 3

HCID 7498Benzyl BromideHCID 24758Sodium hydrideHCID 10866258Pentynol

Product 1

HCID 563055Benzene, [(4-pentynyloxy)methyl]-Yield 94.5%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent

Conditions

Temperature
0 °C

Procedure

To a flame-dried round-bottomed flask was added NaH (2 equiv., 47.6 mmol, 1.9 g of a 60% dispersion in mineral oil). The solid was washed with hexanes (15 mL), THF (95 mL) was added and the suspension was cooled to 0° C. Pentynol (1 equiv., 23.8 mmol, 2.0 g) was added drop wise in THF (5 mL), followed by drop wise addition of BnBr (0.92 equiv., 21.9 mmol, 2.60 mL). The reaction was warmed to ambient temperature over 16 h, quenched with saturated aqueous NH4Cl (25 mL), and diluted with water (20 mL). The organic layer was extracted with EtOAc (2×40 mL), washed with brine (40 mL) and dried with Na2SO4. Product isolation was achieved by concentration in vacuo and purification by flash column chromatography to afford ((pent-4-yn-1-yloxy)methyl)benzene (3.60 g, 20.7 mmol, 94%). TLC Rf=0.41 (5% EtOAc/Hex); 1HNMR (300 MHz): δ 7.29-7.44 (5H), 4.55 (s, 2H), 3.61 (t, 2H, J=6.2 Hz), 2.36 (td, 2H, J=7.1, 2.6 Hz), 1.97 (t, 1H, J=2.6 Hz), 1.81-1.93 (m, 2H). 13CNMR (75 MHz): δ 138.5, 128.4, 127.63, 127.58, 84.0, 73.0, 68.7, 68.5, 28.7, 15.3.

Workup

  1. washThe solid was washed with hexanes (15 mL), THF (95 mL)
  2. additionwas added
  3. temperatureThe reaction was warmed to ambient temperature over 16 h
  4. customquenched with saturated aqueous NH4Cl (25 mL)
  5. additiondiluted with water (20 mL)
  6. extractionThe organic layer was extracted with EtOAc (2×40 mL)
  7. washwashed with brine (40 mL)
  8. dry with materialdried with Na2SO4
  9. concentrationProduct isolation was achieved by concentration in vacuo and purification by flash column chromatography

Sources & evidence

ORD record
ord-1c270ea69f4a471898ae4bfccba67568
Source dataset
uspto-grants-2015_07
Patent number
US09079835B2

Reaction notes

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