Ethyl bromoacetate → HCID 12132636, compound

HRID 393254Notes

Reaction equation

HRID 393254 reaction equation
[C:1]([CH:3]1[C:16]2[CH:15]=[CH:14][CH:13]=[CH:12][C:11]=2[C:10]([CH3:18])([CH3:17])[C:9]2[C:4]1=[CH:5][CH:6]=[CH:7][CH:8]=2)#[N:2].[O-]CC.[Na+].Br[CH2:24][C:25]([O:27][CH2:28][CH3:29])=[O:26]>C(O)C>[CH2:28]([O:27][C:25](=[O:26])[CH2:24][C:3]1([C:1]#[N:2])[C:16]2[CH:15]=[CH:14][CH:13]=[CH:12][C:11]=2[C:10]([CH3:18])([CH3:17])[C:9]2[C:4]1=[CH:5][CH:6]=[CH:7][CH:8]=2)[CH3:29]

Participants

5

Reactant 3

HCID 7748Ethyl bromoacetateHCID 2723922Sodium ethoxideHCID 12132635HCID 12132635, compound

Product 1

HCID 12132636HCID 12132636, compoundYield 89.5%

Reagents, catalysts & solvents 1

HCID 702EthanolSolvent

Procedure

9-cyano-10,10-Dimethyl-9,10-dihydroanthracene [9] (0.8 g, 3.42 mmol) was added to sodium ethoxide prepared from Na metal (0.110 g, 4.80 mmol) and ethanol (10 mL) and heated under reflux for one hour leading to the development of a greenish brown solution. The solution was then cooled in an ice bath and ethyl bromoacetate (0.80 g, 4.80 mmol) was added dropwise via a syringe. The resulting mixture was then heated at reflux (4 h) and filtered. The solid residue was washed with ether (25 mL). Water (25 mL) was added to the filterate and the organic layer was separated. The aqueous layer was once again extracted with ether (25 mL). The combined ether extracts were washed with water, brine, dried (MgSO4) and evaporated under reduced pressure to give an oil which was purified by medium pressure liquid chromatography using pet. ether: EtOAc (9:1) as eluent to give 0.978 g (74%) of the product as a colorless oil. 1H NMR (CDCl3)d: 0.98-1.06 (t, 3H, CH3), 1.64-1.67 (d, J=9Hz, 3H, CH3), 1.71-1.74 (d, J=9 Hz, 3H, CH3), 3.04-3.07 (d, J=9Hz, 2H, CH2), 3.86-3.94 (q, 2H, CH2), 7.29-7.77 (m, 8H, Ar—H). 13C NMR (CDCl3)d: 14.39, 33.85, 35.21, 38.37, 52.29, 61.38, 123.17, 127.53, 127.84, 128.17, 129.48, 130.97, 143.23, 167.97.

Workup

  1. temperatureheated
  2. temperatureunder reflux for one hour
  3. temperatureThe solution was then cooled in an ice bath
  4. temperatureThe resulting mixture was then heated
  5. temperatureat reflux (4 h)
  6. filtrationfiltered
  7. washThe solid residue was washed with ether (25 mL)
  8. additionWater (25 mL) was added to the filterate
  9. customthe organic layer was separated
  10. extractionThe aqueous layer was once again extracted with ether (25 mL)
  11. washThe combined ether extracts were washed with water, brine
  12. dry with materialdried (MgSO4)
  13. customevaporated under reduced pressure
  14. customto give an oil which
  15. customwas purified by medium pressure liquid chromatography

Sources & evidence

ORD record
ord-ec78969bb4404c739bf4255e95b76e5d
Source dataset
uspto-grants-2004_10
Patent number
US06806283B2

Reaction notes

Loading…