Acetic Acid → HCID 15077393, compound

HRID 2165726Notes

Reaction equation

HRID 2165726 reaction equation
[Na].[C:2]([CH2:4][C:5]([O:7][CH2:8][CH3:9])=[O:6])#[N:3].Br[CH2:11][CH2:12][CH2:13][CH2:14][N:15]([S:27]([C:30]1[CH:36]=[CH:35][C:33]([CH3:34])=[CH:32][CH:31]=1)(=[O:29])=[O:28])[C:16]1[CH:26]=[CH:25][C:19]([C:20]([O:22][CH2:23][CH3:24])=[O:21])=[CH:18][CH:17]=1.C(O)(=O)C>C(O)C.C(OCC)(=O)C>[C:2]([CH:4]([C:5]([O:7][CH2:8][CH3:9])=[O:6])[CH2:11][CH2:12][CH2:13][CH2:14][N:15]([S:27]([C:30]1[CH:31]=[CH:32][C:33]([CH3:34])=[CH:35][CH:36]=1)(=[O:28])=[O:29])[C:16]1[CH:17]=[CH:18][C:19]([C:20]([O:22][CH2:23][CH3:24])=[O:21])=[CH:25][CH:26]=1)#[N:3]

Participants

7

Reactant 4

HCID 176Acetic AcidHCID 7764Ethyl cyanoacetateHCID 5360545SodiumHCID 15077392HCID 15077392, compound

Product 1

HCID 15077393HCID 15077393, compound

Reagents, catalysts & solvents 2

HCID 702EthanolSolvent2×HCID 8857Ethyl AcetateSolvent

Procedure

A mixture of 0.506 g (0.0220 mol) of sodium in 10 mL of absolute ethanol under nitrogen was refluxed briefly, and a solution formed. After it had cooled to room temperature, to the solution was added dropwise over a 2-min period 2.74 g (0.0242 mol) of ethyl cyanoacetate. The mixture was refluxed for 10 min and was allowed to cool to room temperature. Then to it was added over a 6-min period 5.00 g (0.0110 mol) of ethyl 4-[(4-bromobutyl)tosylamino]benzoate and 15 mL of rinse absolute ethanol. The mixture was refluxed under nitrogen for 6 h, allowed to cool to room temperature, and stand overnight. It was neutralized with glacial acetic acid and concentrated under vacuum to a wet solid to which was added 50 mL of water and 50 mL of ether. The mixture was shaken in a separatory funnel, and the layers were separated. The aqueous layer was washed with 2×50 mL more ether, and the ether washes were combined, dried over magnesium sulfate for three days, filtered, and concentrated under high vacuum at 60° C. to a viscous, pink oil; yield, 5.97 g. The oil was purified by a flash chromatography column consisting of 400 g of Silica Gel 60 with 3:1 hexanes/ethyl acetate as the eluting solvent. Fractions containing clean product were combined and concentrated under vacuum to a colorless, viscous oil; yield, 2.76 g (50%): NMR (Me2SOd6) δ 1.19 (t, 3H), 1.29 (t, 3H), 1.3-1.5 (m, 4H), 1.65-1.85 (m, 2H), 2.37 (s, 3H), 3.5-3.7 (m, 2H), 4.14 (t, 1H), 4.15 (q, 2H), 4.29 (q, 2H), 7.22 (d, 2H), 7.3-7.5 (AA'BB', 4H), 7.90 (d, 2H), 0.15 mol of ethyl acetate.

Workup

  1. temperaturewas refluxed briefly
  2. customa solution formed
  3. temperatureThe mixture was refluxed for 10 min
  4. temperatureto cool to room temperature
  5. temperatureThe mixture was refluxed under nitrogen for 6 h
  6. temperatureto cool to room temperature
  7. concentrationconcentrated under vacuum to a wet solid to which
  8. additionwas added 50 mL of water and 50 mL of ether
  9. customthe layers were separated
  10. washThe aqueous layer was washed with 2×50 mL more ether
  11. dry with materialdried over magnesium sulfate for three days
  12. filtrationfiltered
  13. concentrationconcentrated under high vacuum at 60° C. to a viscous, pink oil
  14. customyield
  15. customThe oil was purified by a flash chromatography column
  16. additionFractions containing clean product
  17. concentrationconcentrated under vacuum to a colorless, viscous oil
  18. customyield

Sources & evidence

ORD record
ord-52930fd0eed44080b32ff6f360a6af3c
Source dataset
uspto-grants-1990_07
Patent number
US04940713

Reaction notes

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