Allyl bromide → 2-[(Prop-2-en-1-yloxy)methyl]cyclohexanone

HRID 73624Notes

Reaction equation

HRID 73624 reaction equation
[H-].[Na+].[O:3]1[C:7]2([CH2:12][CH2:11][CH2:10][CH2:9][CH:8]2[CH2:13][OH:14])OCC1.[CH2:15](Br)[CH:16]=[CH2:17]>C1COCC1>[CH2:17]([O:14][CH2:13][CH:8]1[CH2:9][CH2:10][CH2:11][CH2:12][C:7]1=[O:3])[CH:16]=[CH2:15]

Participants

5

Reactant 3

HCID 7841Allyl bromideHCID 24758Sodium hydrideHCID 40665581,4-Dioxaspiro[4.5]decan-6-ylmethanol

Product 1

HCID 107022592-[(Prop-2-en-1-yloxy)methyl]cyclohexanone

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent2×

Procedure

To a mixture of NaH (1.14 g, 60% oil dispersion, 28.6 mmol) in dry THF (45 mL) at 0° C. was added 1,4-dioxaspiro[4.5]dec-6-ylmethanol (2.46 g, 14.3 mmol) in dry THF (5 mL). The mixture was allowed to warm to rt and stirred for 1 hr. The mixture was then cooled to 0° C. and allyl bromide (2.10 mL, 24.28 mmol) was added in one portion. The mixture was then allowed to warm to rt and stirred for 1 hr. The mixture was then heated to 60° C. overnight. It was cooled to 0° C. and quenched with 50 mL of 10% aq HCl. This mixture was stirred for 1 hr at rt. The resulting mixture was cooled to 0° C. and neutralized carefully with solid Na2CO3 and then extracted with Et2O. The combined organics were dried, filtered, and concentrated. The residue was purified by column chromatography to give the title compound. 1H NMR (500 MHz, CDCl3) δ 5.86-5.95 (m, 1H), 5.28 (d, 1H, J=1.7 Hz), 5.25 (d, 1H, J=1.5 Hz), 5.17 (d, 1H, J=10.5 Hz), 3.94-4.03 (m, 2H), 3.79 (dd, 1H, J=5.1 Hz, 9.8 Hz), 3.38 (dd, 1H, J=7.33 Hz, 9.53 Hz), 2.56-2.65 (m, 1H), 2.26-2.43 (m, 3H), 2.02-2.10 (m, 1H), 1.85-1.93 (m, 1H), 1.61-1.74 (m, 2H), 1.39-1.49 (m, 1H).

Workup

  1. temperatureThe mixture was then cooled to 0° C.
  2. temperatureto warm to rt
  3. stirringstirred for 1 hr
  4. temperatureThe mixture was then heated to 60° C. overnight
  5. temperatureIt was cooled to 0° C.
  6. customquenched with 50 mL of 10% aq HCl
  7. stirringThis mixture was stirred for 1 hr at rt
  8. temperatureThe resulting mixture was cooled to 0° C. and neutralized carefully with solid Na2CO3
  9. extractionextracted with Et2O
  10. customThe combined organics were dried
  11. filtrationfiltered
  12. concentrationconcentrated
  13. customThe residue was purified by column chromatography

Sources & evidence

ORD record
ord-bc7e5413d6884d33a826f37120b42ee5
Source dataset
uspto-grants-2014_09
Patent number
US08829196B2

Reaction notes

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