Allyl bromide → HCID 10489752, compound

HRID 2111456Notes

Reaction equation

HRID 2111456 reaction equation
Br[C:2]1[CH:7]=[CH:6][C:5]([CH:8]2[O:13][CH2:12][C:11]([CH3:15])([CH3:14])[CH2:10][O:9]2)=[CH:4][CH:3]=1.[Mg].[CH2:17](Br)[CH:18]=[CH2:19]>C1COCC1>[CH2:19]([C:2]1[CH:7]=[CH:6][C:5]([CH:8]2[O:13][CH2:12][C:11]([CH3:15])([CH3:14])[CH2:10][O:9]2)=[CH:4][CH:3]=1)[CH:18]=[CH2:17]

Participants

5

Reactant 3

HCID 7841Allyl bromideHCID 5462224MagnesiumHCID 137145152-(4-Bromophenyl)-5,5-dimethyl-1,3-dioxane

Product 1

HCID 10489752HCID 10489752, compoundYield 59%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent2×

Procedure

In a dry apparatus a solution of 12 (2.05 g, 7.60 mmol) in THF (15 mL) was added dropwise to magnesium powder (0.22 g, 9.1 mmol) under argon. After the addition was completed the mixture was refluxed for 45 min. Then the mixture was cooled to rt and allyl bromide (720 μL, 8.30 mmol) dissolved in THF (10 mL) was added slowly. The mixture was stirred for 4.5 h, then quenched with satd aq NH4Cl (25 mL) and extracted with ether. The combined organic phases were washed with aq NaHCO3 (5%) and brine and dried (Na2SO4). The solvents were removed under reduced pressure and the residue was crystallized from hexanes and filtered. The filtrate was purified by column chromatography (silica, ether/hexanes, 1:4), affording a light yellow oil (1.04 g, 59%). IR (neat): {tilde over (v)} 3077, 2955, 2904, 2846, 1639, 1619, 1517; 1H NMR δ 0.79 (s, 3H), 1.29 (s, 3H), 3.38 (d, 3J=6.6 Hz, 2H), 3.64 (d, 2J=11.0 Hz, 2H), 3.76 (d, 2J=11.0 Hz, 2H), 5.00-5.10 (m, 2H), 5.37 (s, 1H), 5.86-6.01 (m, 1H), 7.19, 7.43 (AA′BB′, 2×2H); 13C NMR (APT) δ 21.7 (−), 22.9 (−), 30.0 (+), 39.8 (+), 77.5 (+), 101.5 (−), 115.6 (+), 126.1 (−), 128.4 (−), 136.3 (+), 137.2 (−), 140.5 (+); GC-MS (EI) obsd 232, 231, 191, 163, 145, 115, 105, 91, 69, 56, 41; Anal. Calcd for C15H20O2: C, 77.55; H, 8.68. Found: C, 77.52; H, 8.77.

Workup

  1. additionAfter the addition
  2. temperaturewas refluxed for 45 min
  3. additionwas added slowly
  4. customquenched with satd aq NH4Cl (25 mL)
  5. extractionextracted with ether
  6. washThe combined organic phases were washed with aq NaHCO3 (5%) and brine
  7. dry with materialdried (Na2SO4)
  8. customThe solvents were removed under reduced pressure
  9. customthe residue was crystallized from hexanes
  10. filtrationfiltered
  11. customThe filtrate was purified by column chromatography (silica, ether/hexanes, 1:4)

Sources & evidence

ORD record
ord-30705d7ea9eb4e6da40d2c7ccbc5c4de
Source dataset
uspto-grants-2009_04
Patent number
US07518905B2

Reaction notes

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