Ethyl vinyl ether → HCID 44550638, compound

HRID 2068171Notes

Reaction equation

HRID 2068171 reaction equation
[Br:1]Br.[CH:3]([O:5][CH2:6][CH3:7])=[CH2:4].C(N(C(C)C)CC)(C)C.[C:17]([Si:21]([CH3:41])([CH3:40])[O:22][C:23]1[CH:28]=[CH:27][C:26]([C:29]2[C:30]([CH:38]=[O:39])=[CH:31][CH:32]=[C:33]([O:36][CH3:37])[C:34]=2[OH:35])=[CH:25][CH:24]=1)([CH3:20])([CH3:19])[CH3:18]>C(Cl)Cl>[Br:1][CH2:4][CH:3]([O:5][CH2:6][CH3:7])[O:35][C:34]1[C:33]([O:36][CH3:37])=[CH:32][CH:31]=[C:30]([CH:38]=[O:39])[C:29]=1[C:26]1[CH:25]=[CH:24][C:23]([O:22][Si:21]([C:17]([CH3:20])([CH3:19])[CH3:18])([CH3:41])[CH3:40])=[CH:28][CH:27]=1

Participants

6

Reactant 4

HCID 8023Ethyl vinyl etherHCID 24408BromineHCID 81531DiisopropylethylamineHCID 86647716HCID 86647716, compound

Product 1

HCID 44550638HCID 44550638, compoundYield 97.4%

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent2×

Procedure

To a solution of Br2 (0.397 mL, 7.74 mmol) in CH2Cl2 (30 mL) at 0° C. was added drop-wise ethyl vinyl ether (0.92 mL, 9.68 mmol) until the solution turned colorless. The mixture was stirred for 15 min and diisopropylethyamine (2.71 mL, 15.48 mmol) was added followed by a drop-wise addition of a solution of 11 (1.5 g, 3.87 mmol) in CH2Cl2 (15 mL) The mixture was stirred for 12 h under an argon atmosphere to give an orange-red solution. After complete consumption of staring material, as determined by TLC. the mixture was poured onto saturated aqueous NaHCO3 and extracted with CH2Cl2 (3×50 mL). The combined extracts were washed with brine (100 mL), dried (Na2SO4), filtered and evaporated in vacuo to give an orange-red oil. Purification by flash column chromatography (SiO2, 10% EtOAc/Hexanes) gave 13 (1.92 g, 92% yield) as a colorless syrupy liquid. (1.92 g, 92% yield). Rf=0.42 (1:5 EtOAc/hexanes). IR (thin film) 2956, 2930, 2857, 1684 cm−1. 1H NMR (300 MHz, CDCl3) δ 9.64 (1H, s), 7.85 (1H, d, J=9 Hz), 7.25-7.18 (2H, m), 7.03 (1H, d, J=9 Hz), 6.93 (2H, d, J=9 Hz), 5.01 (1H, dd, J's=7, 4 Hz), 3.98 (3H, s), 3.56 (1H, m), 3.31 (1H, m), 3.09 (2H, m), 1.05 (2H, t, 7 Hz), 1.01 (9H, s), 0.24 (6H, s). 13C NMR (75 MHz, CDCl3) δ 191.5, 157.02, 155.8, 141.7, 140.6, 132.5, 128.5, 125.2, 119.7, 111.0, 103.7, 64.5, 55.9, 31.8, 25.6, 18.2, 14.9, −4.4. HRMS calcd. for C24H34O5SiBr (MH+) 509.1359. Found 509.1356.

Workup

  1. stirringwas stirred for 12 h under an argon atmosphere
  2. customto give an orange-red solution
  3. customAfter complete consumption of staring material
  4. additionthe mixture was poured onto saturated aqueous NaHCO3
  5. extractionextracted with CH2Cl2 (3×50 mL)
  6. washThe combined extracts were washed with brine (100 mL)
  7. dry with materialdried (Na2SO4)
  8. filtrationfiltered
  9. customevaporated in vacuo
  10. customto give an orange-red oil
  11. customPurification by flash column chromatography (SiO2, 10% EtOAc/Hexanes)

Sources & evidence

ORD record
ord-334bbc4c3531451e874990498a4a4d33
Source dataset
uspto-grants-2012_10
Patent number
US08293927B2

Reaction notes

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