1-Ethynylcyclohexanol → Cyclohexane, 1-ethynyl-1-(2-propenyloxy)-

HRID 921085Notes

Reaction equation

HRID 921085 reaction equation
[C:1]([C:3]1([OH:9])[CH2:8][CH2:7][CH2:6][CH2:5][CH2:4]1)#[CH:2].[H-].[Na+].[CH2:12](Br)[CH:13]=[CH2:14]>CN(C=O)C.CCOCC>[CH2:14]([O:9][C:3]1([C:1]#[CH:2])[CH2:8][CH2:7][CH2:6][CH2:5][CH2:4]1)[CH:13]=[CH2:12]

Participants

6

Reactant 3

HCID 65251-EthynylcyclohexanolHCID 7841Allyl bromideHCID 24758Sodium hydride

Product 1

HCID 11051992Cyclohexane, 1-ethynyl-1-(2-propenyloxy)-Yield 66.7%

Reagents, catalysts & solvents 2

HCID 3283Diethyl EtherSolventHCID 6228DimethylformamideSolvent

Procedure

A solution of 1-ethynylcyclohexanol (2.28 g, 18.36 mmol) in DMF (25 ml) was cooled (0° C. ice bath) and treated with 60% NaH (0.890 g, 22.25 mmol). The reaction was stirred for 30 min, then warmed to room temperature and stirred for 1 hr. To this was added allyl bromide (4.8 ml, 55.5 mmol) over 5 min and continued stirring for 16 h. The reaction was diluted with Et2O (75 mL), washed with water (4×50 mL), brine (50 mL), dried (MgSO4), filtered and concentrated to give the product, 1-(allyloxy)-1-ethynylcyclohexane (2.873 g, 12.24 mmol, 66.7% yield) as a pale yellow mobile oil. 1H NMR consistent with expected product, consists of approx 3:1 product/SM. Used as-is without further purification 1H NMR (CDCl3) δ: 5.94-6.04 (m, 1H), 5.33 (dq, J=17.2, 1.7 Hz, 1H), 5.17 (dq, J=10.3, 1.5 Hz, 1H), 4.15 (dt, J=5.6, 1.5 Hz, 2H), 2.50 (s, 1H), 2.49 (s, 1H), 1.91-1.98 (m, 3H), 1.49-1.77 (m, 12H), 1.24-1.38 (m, 3H).

Workup

  1. stirringstirred for 1 hr
  2. stirringcontinued stirring for 16 h
  3. washwashed with water (4×50 mL), brine (50 mL)
  4. dry with materialdried (MgSO4)
  5. filtrationfiltered
  6. concentrationconcentrated

Sources & evidence

ORD record
ord-9ed3fe2d41dd480faea81ba97ac9b752
Source dataset
uspto-grants-2016_03
Patent number
US09273067B2

Reaction notes

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