Hydrochloric Acid → HCID 54534282, compound

HRID 2258690Notes

Reaction equation

HRID 2258690 reaction equation
[CH2:1]([O:3][C:4]([C:6]([CH2:19][C:20]([C:22]1[CH:27]=[CH:26][C:25]([N+:28]([O-:30])=[O:29])=[CH:24][CH:23]=1)=[O:21])([CH2:12][CH2:13][C:14]([O:16][CH2:17][CH3:18])=[O:15])C(OCC)=O)=[O:5])[CH3:2].[OH-].[Na+].Cl>C(O)C>[N+:28]([C:25]1[CH:24]=[CH:23][C:22]([C:20](=[O:21])[CH2:19][CH:6]([CH2:12][CH2:13][C:14]([O:16][CH2:17][CH3:18])=[O:15])[C:4]([O:3][CH2:1][CH3:2])=[O:5])=[CH:27][CH:26]=1)([O-:30])=[O:29]

Participants

5

Reactant 3

HCID 313Hydrochloric AcidHCID 14798Sodium HydroxideHCID 23507977HCID 23507977, compound

Product 1

HCID 54534282HCID 54534282, compoundYield 71.9%

Reagents, catalysts & solvents 1

HCID 702EthanolSolvent

Procedure

A solution of diethyl 2-ethoxycarbonyl-2-(2-(4-nitrophenyl)-2-oxoethyl)glutarate (2.5 g, 5.9 mmol) in ethanol:1N NaOH (2:1, 105 ml) was stirred 20 hours at room temperature and then acidified to pH 1.5 with concentrated HCl and concentrated in vacuo. The residue was dissolved in diglyme (50 ml) and the solution stirred at reflux for 20 minutes and then concentrated in vacuo. The residue was then dissolved in ethanol (50 ml). HCl gas was bubbled into the solution for 30 seconds, and the solution was stirred at room temperature over the weekend and then concentrated in vacuo. The product was taken up in diethyl ether (100 ml), washed with saturated sodium bicarbonate solution (35 ml), dried (MgSO4), and concentrated in vacuo. Purification by chromatography on silica gel eluting with ethyl acetate:hexane (1:4) gave diethyl (RS)-2-(2-(4-nitrophenyl)-2-oxoethyl)glutarate (1.49 g) as an oil 1H NMR (DMSO-d6, 200 MHz) δ: 1.13 (t, J=7 Hz, 3H, CH3), 1.19 (t, J=7 Hz, 3H, CH3), 1.74-1.93 (m, 2H, CH2), 2.35-2.45 (m, 2H, CH2CO2), 2.82-3.00 (m, 1H, CH), 3.24-3.67 (m, 2H, COCH2), 4.03 (q, J=7 Hz, 2H, ester CH2), 4.04 (q, J=7 Hz, 2H, ester CH2), 8.20 (d, J=9 Hz, 2H, Ar), 8.33 (d, J=9 Hz, 2H, Ar). Anal. Calculated for C17H21NO7.1/4H2O: C, 57.38; H, 6.09; N, 3.94. Found: C, 57.35; H, 6.11; N, 3.89.

Workup

  1. concentrationconcentrated in vacuo
  2. dissolutionThe residue was dissolved in diglyme (50 ml)
  3. temperatureat reflux for 20 minutes
  4. concentrationconcentrated in vacuo
  5. dissolutionThe residue was then dissolved in ethanol (50 ml)
  6. customHCl gas was bubbled into the solution for 30 seconds
  7. stirringthe solution was stirred at room temperature over the weekend
  8. concentrationconcentrated in vacuo
  9. washwashed with saturated sodium bicarbonate solution (35 ml)
  10. dry with materialdried (MgSO4)
  11. concentrationconcentrated in vacuo
  12. customPurification by chromatography on silica gel eluting with ethyl acetate:hexane (1:4)

Sources & evidence

ORD record
ord-8964197074a9416a9915f977f79477c4
Source dataset
uspto-grants-1997_08
Patent number
US05661155

Reaction notes

Loading…