Diethyl Ether → HCID 4313443, compound

HRID 1609382Notes

Reaction equation

HRID 1609382 reaction equation
[Se](=O)=[O:2].[CH:4]1[C:9]([C:10]([CH2:12]Br)=[O:11])=[CH:8][CH:7]=[C:6]([Cl:14])[CH:5]=1.CC[O:17][CH2:18]C>CO>[Cl:14][C:6]1[CH:7]=[CH:8][C:9]([C:10](=[O:11])[C:12]([O:17][CH3:18])=[O:2])=[CH:4][CH:5]=1

Participants

5

Reactant 3

HCID 3283Diethyl EtherHCID 24007Selenium DioxideHCID 68303p-Chlorophenacyl bromide

Product 1

HCID 4313443HCID 4313443, compoundYield 35%

Reagents, catalysts & solvents 1

HCID 887MethanolSolvent

Procedure

Selenium dioxide (35.5 g; 320 mmol) was dissolved in 250 mL of MeOH (warm to reflux with stirring), and 19.6 g (315 mmol) of α-bromo-4-chloroacetophenone was added. The reaction mixture was warmed to reflux for 24 hours, cooled, filtered and concentrated leaving an orange oil. The oil was diluted with 1500 mL of Et2O and washed three times with 200 mL of H2O and once with 200 mL of brine, dried (Na2SO4) and concentrated. The crude oil was crystallized from Et2O and hexanes at -20° C. The white needles were filtered while cold and washed with small portions of cold hexanes to yield 22 g (35%) of methyl p-chlorophenyl-α-oxoacetate, m.p. 56°-57° C., 1H-NMR (CDCl3)δ8.0-7.9 (m, 2H), 7.5-7.4 (m, 2H), 3.9 (s, 3H); 13C-NMR (CDCl3)δ184.4, 163.5, 141.6, 131.4, 131.0, 129.3, 52.7.

Workup

  1. temperatureThe reaction mixture was warmed
  2. temperatureto reflux for 24 hours
  3. temperaturecooled
  4. filtrationfiltered
  5. concentrationconcentrated
  6. customleaving an orange oil
  7. washwashed three times with 200 mL of H2O
  8. dry with materialonce with 200 mL of brine, dried (Na2SO4)
  9. concentrationconcentrated
  10. customThe crude oil was crystallized from Et2O and hexanes at -20° C
  11. filtrationThe white needles were filtered while cold and
  12. washwashed with small portions of cold hexanes

Sources & evidence

ORD record
ord-d58ce972024947d3bfdc444739ecc02f
Source dataset
uspto-grants-1995_03
Patent number
US05399721

Reaction notes

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