Acetic Acid → HCID 10679379, compound

HRID 1375089Notes

Reaction equation

HRID 1375089 reaction equation
[O:1]1[CH2:6][CH2:5][C:4](=O)[CH2:3][CH2:2]1.[CH2:8]([O:10][C:11](=[O:15])[CH2:12][C:13]#[N:14])[CH3:9].C([O-])(=O)C.[NH4+].C(O)(=O)C>C1(C)C=CC=CC=1.N1CCCCC1.O>[CH2:8]([O:10][C:11](=[O:15])[C:12]([C:13]#[N:14])=[C:4]1[CH2:5][CH2:6][O:1][CH2:2][CH2:3]1)[CH3:9]

Participants

8

Reactant 4

HCID 176Acetic AcidHCID 7764Ethyl cyanoacetateHCID 121599Tetrahydro-4H-pyran-4-oneHCID 517165Ammonium Acetate

Product 1

HCID 10679379HCID 10679379, compound

Reagents, catalysts & solvents 3

HCID 8082PiperidineCatalystHCID 962WaterSolventHCID 1140TolueneSolvent

Procedure

A stirred solution of tetrahydro-pyran-4-one (5 g) in toluene (50 mL) was treated sequentially with cyano-acetic acid ethyl ester (5.3 mL), ammonium acetate (0.7 g), acetic acid (2.2 mL) and piperidine (3 drops) then stirred at reflux temperature for 3.5 hours and then stood at room temperature for 3 days. The reaction mixture was evaporated to give a red oil, which solidified on standing at room temperature. This solid was treated with water (30 mL) and the mixture was extracted with ethyl acetate (50 mL). The extract was washed with saturated aqueous sodium bicarbonate solution (30 mL), then with water (30 mL), then dried over magnesium sulfate and then evaporated. The residual pale yellow waxy solid (8.92 g) was refluxed with petroleum ether (b.p. 80–100° C.) when partial solution was achieved. This mixture was treated with cyclohexane (20 mL) and then decanted to remove a small amount of brown gum. The decanted solution was stood at room temperature overnight and the resulting crystalline pale yellow solid was filtered then washed with pentane and then dried at 40° C. under vacuum to give the title compound (5.10 g) as a pale yellow crystalline solid. LC-MS: RT=2.85 minutes, MS(ES+): 169(M+H)+, MS(ES−): 194(M−H)−.

Workup

  1. temperatureat reflux temperature for 3.5 hours
  2. customThe reaction mixture was evaporated
  3. customto give a red oil, which
  4. customon standing at room temperature
  5. extractionthe mixture was extracted with ethyl acetate (50 mL)
  6. washThe extract was washed with saturated aqueous sodium bicarbonate solution (30 mL)
  7. dry with materialwith water (30 mL), then dried over magnesium sulfate
  8. customevaporated
  9. temperatureThe residual pale yellow waxy solid (8.92 g) was refluxed with petroleum ether (b.p. 80–100° C.) when partial solution
  10. additionThis mixture was treated with cyclohexane (20 mL)
  11. customdecanted
  12. customto remove a small amount of brown gum
  13. waitThe decanted solution was stood at room temperature overnight
  14. filtrationthe resulting crystalline pale yellow solid was filtered
  15. washthen washed with pentane
  16. customdried at 40° C. under vacuum

Sources & evidence

ORD record
ord-c42475c8b6564dd79e6d832b2d676b93
Source dataset
uspto-grants-2007_01
Patent number
US07166616B2

Reaction notes

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