Acetic Acid → Methyl cyano(oxan-4-ylidene)acetate

HRID 76213Notes

Reaction equation

HRID 76213 reaction equation
[O:1]1[CH2:6][CH2:5][C:4](=O)[CH2:3][CH2:2]1.[C:8]([CH2:10][C:11]([O:13][CH3:14])=[O:12])#[N:9].C([O-])(=O)C.[NH4+].C(O)(=O)C>O.C1C=CC=CC=1>[C:8]([C:10](=[C:4]1[CH2:5][CH2:6][O:1][CH2:2][CH2:3]1)[C:11]([O:13][CH3:14])=[O:12])#[N:9]

Participants

7

Reactant 4

HCID 176Acetic AcidHCID 7747Methyl cyanoacetateHCID 121599Tetrahydro-4H-pyran-4-oneHCID 517165Ammonium Acetate

Product 1

HCID 11052260Methyl cyano(oxan-4-ylidene)acetate

Reagents, catalysts & solvents 2

HCID 241BenzeneSolventHCID 962WaterSolvent

Procedure

A 50 ml round-bottom flask equipped with a Dean-Stark distillation setup and condenser was charged with tetrahydro-4H-pyran-4-one (4.61 ml, 50 mmol), methyl cyanoacetate (5.3 ml, 60 mmol), ammonium acetate (1 g, 13 mmol), acetic acid (0.57 ml, 10 mmol) and benzene (30 ml). The mixture was refluxed until no more water collected in the Dean-Stark (2 hours), cooled, benzene (30 ml) added and the organic layer washed with water (50 ml). The aqueous layer was extracted with CH2Cl2 (3×50 ml). The combined organic phase was washed with sat. NaHCO3 (100 ml), brine (100 ml) dried (MgSO4), filtered and concentrated. Purified by normal phase SiO2 chromatography (10 to 60% EtOAc/hexanes) to afford methyl 2-cyano-2-(oxan-4-ylidene)acetate as a colorless oil (6.30 g, 70%, m/z: 181.1 [M+H]+ observed).

Workup

  1. customA 50 ml round-bottom flask equipped with a Dean-Stark distillation setup and condenser
  2. customcollected in the Dean-Stark (2 hours)
  3. temperaturecooled
  4. additionbenzene (30 ml) added
  5. washthe organic layer washed with water (50 ml)
  6. extractionThe aqueous layer was extracted with CH2Cl2 (3×50 ml)
  7. washThe combined organic phase was washed with sat. NaHCO3 (100 ml), brine (100 ml)
  8. dry with materialdried (MgSO4)
  9. filtrationfiltered
  10. concentrationconcentrated
  11. customPurified by normal phase SiO2 chromatography (10 to 60% EtOAc/hexanes)

Sources & evidence

ORD record
ord-0f882151bfef4da4a3b36c7ee3d441b5
Source dataset
uspto-grants-2014_09
Patent number
US08835488B2

Reaction notes

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