Hydrochloric Acid → HCID 54691693, compound

HRID 1034217Notes

Reaction equation

HRID 1034217 reaction equation
[CH2:1]([NH2:6])[CH2:2][CH2:3][CH2:4][CH3:5].[Na].[C:8]([O:12][C:13]([CH3:16])([CH3:15])[CH3:14])(=[O:11])C=C.C(OCC)(=O)[C:18](OCC)=[O:19].[O-:27][CH2:28][CH3:29].[Na+].Cl.[CH3:32]CO>O>[OH:27][C:28]1[C:18](=[O:19])[N:6]([CH2:1][CH2:2][CH2:3][CH2:4][CH3:5])[CH2:32][C:29]=1[C:8]([O:12][C:13]([CH3:16])([CH3:15])[CH3:14])=[O:11]

Participants

9

Reactant 7

HCID 313Hydrochloric AcidHCID 702EthanolHCID 7268Diethyl OxalateHCID 8060PentylamineHCID 15458tert-Butyl acrylateHCID 2723922Sodium ethoxideHCID 5360545Sodium2×

Product 1

HCID 54691693HCID 54691693, compoundYield 47%

Reagents, catalysts & solvents 1

HCID 962WaterSolvent

Procedure

To a solution of n-pentyl amine (21.72 g, 0.25 mol) in 110 ml of EtOH (freshly distilled from sodium) was added tert-butyl acrylate (36.62 ml, 0.26 mol) via syringe and the resulting solution was stirred under an atmosphere of argon for 12 h at room temperature. To the solution was then added diethyl oxalate (36.54 g, 0.25 mol). The solution was then cooled to 0° C. and a freshly prepared solution of sodium ethoxide (from 5.75 g (.25 mole) of sodium and 75 ml of EtOH) was added via cannula while maintaining the temperature between 0° C. and 5° C. After the addition was complete, the solution was allowed to warm to room temperature and stirred overnight. To the resulting slurry was added 400 ml of water followed the slow addition of 30% aqueous HCl to acidify to pH=4. The suspension was then extracted with CH2Cl2. The organic phase was dried over MgSO4, filtered, and concentrated in vacuo to give a white solid. Recrystallization from ethyl acetate gave the title compound (31.57 g, 47%) as a colorless powder. Anal calcd for C14H23NO4 1/4H2O: C, 61.40; H, 8.65; N, 5.11. Found: C, 61.38; H, 8.54; N, 5.22. MS M+1 calcd for C14H23NO4 270, found 270. DSC=102.3°-106.4° C. at 101.7 J/g. Chromatography of the mother liquor on silica gel eluting with EtOH/CH2Cl2 /HOAc (2/98/1) gave an additional 17.5 g (26%) of the title compound.

Workup

  1. temperatureThe solution was then cooled to 0° C.
  2. temperaturewhile maintaining the temperature between 0° C. and 5° C
  3. additionAfter the addition
  4. temperatureto warm to room temperature
  5. stirringstirred overnight
  6. extractionThe suspension was then extracted with CH2Cl2
  7. dry with materialThe organic phase was dried over MgSO4
  8. filtrationfiltered
  9. concentrationconcentrated in vacuo
  10. customto give a white solid
  11. customRecrystallization from ethyl acetate

Sources & evidence

ORD record
ord-9c8205647db94166b5a821a8bd37f378
Source dataset
uspto-grants-1994_05
Patent number
US05314886

Reaction notes

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