Homoallyl bromide → Diethyl 3-butenylphosphonate

HRID 373884Notes

Reaction equation

HRID 373884 reaction equation
[P:1]([O-:8])([O:5][CH2:6][CH3:7])[O:2][CH2:3][CH3:4].[H-].[Na+].Br[CH2:12][CH2:13][CH:14]=[CH2:15]>O1CCCC1>[CH2:15]([P:1](=[O:8])([O:5][CH2:6][CH3:7])[O:2][CH2:3][CH3:4])[CH2:14][CH:13]=[CH2:12]

Participants

5

Reactant 3

HCID 21241Homoallyl bromideHCID 24758Sodium hydrideHCID 3780918Diethylphosphite

Product 1

HCID 10997850Diethyl 3-butenylphosphonateYield 67%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent

Procedure

Diethyl phosphite (4.14 g, 0.03 mol) was added to a suspension of 60% sodium hydride (1.2 g, 0.03 mol) in dry tetrahydrofuran (60 ml) at ambient temperature. The mixture was stirred for 5 minutes until a pale yellow solution was obtained. 4-Bromobut-1-ene (4.5 g, 0.033 mol) was added dropwise and the reaction mixture heated at reflux for 3 hours. After cooling to ambient temperature and filtering, the filtrate was concentrated under reduced pressure to give an oil. The oil was chromatographed on silica gel (eluting with ethyl acetate-hexane, 50:50) to yield the title compound as a colorless oil (3.85 g, 67%). IR: υmax (film) 3080, 3000, 2940, 2920, 2880, 1645, 1450, 1390, 1260, 1165, 1060, 1030, 970, 820, 790 cm-1. 1H NMR: δH (CDCl3) 1.35 (6H, t, J=7Hz, (OCH2CH3)2), 1.50-2.70 (4H, m, CH2CH2P), 4.10 (4H, m, (OCH2CH3)2) 4.85-5.28 (2H, m, CH2 =CH), 5.5-6.28 (1H, m, CH2 =CH--CH2).

Workup

  1. customwas obtained
  2. temperaturethe reaction mixture heated
  3. temperatureat reflux for 3 hours
  4. filtrationfiltering
  5. concentrationthe filtrate was concentrated under reduced pressure
  6. customto give an oil
  7. customThe oil was chromatographed on silica gel (eluting with ethyl acetate-hexane, 50:50)

Sources & evidence

ORD record
ord-5b7fde014689438992840fad551604d9
Source dataset
uspto-grants-1992_11
Patent number
US05166198

Reaction notes

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