Acetic Acid → Methyl 2-cyano-2-(6-oxaspiro[4.5]decan-9-ylidene)acetate

HRID 626479Notes

Reaction equation

HRID 626479 reaction equation
[CH2:1]1[C:5]2([CH2:10][C:9](=O)[CH2:8][CH2:7][O:6]2)[CH2:4][CH2:3][CH2:2]1.[C:12]([CH2:14][C:15]([O:17][CH3:18])=[O:16])#[N:13].C([O-])(=O)C.[NH4+].C(O)(=O)C>O.C1C=CC=CC=1>[C:12](/[C:14](=[C:9]1\[CH2:8][CH2:7][O:6][C:5]2([CH2:10]\1)[CH2:4][CH2:3][CH2:2][CH2:1]2)/[C:15]([O:17][CH3:18])=[O:16])#[N:13]

Participants

7

Reactant 4

HCID 176Acetic AcidHCID 7747Methyl cyanoacetateHCID 517165Ammonium AcetateHCID 641064636-Oxaspiro[4.5]decan-9-one

Product 1

HCID 68313883Methyl 2-cyano-2-(6-oxaspiro[4.5]decan-9-ylidene)acetate

Reagents, catalysts & solvents 2

HCID 241BenzeneSolventHCID 962WaterSolvent

Procedure

A 100 ml round-bottom flask equipped with a Dean-Stark distillation setup and condenser was charged with 6-oxaspiro[4.5]decan-9-one (6 g, 39 mmol, which was prepared according to Hanschke, E. Chem. Ber. 1955, 88, 1053), methyl cyanoacetate (4.1 ml, 46.7 mmol), ammonium acetate (780 mg, 10.1 mmol), acetic acid (0.44 ml, 7.8 mmol) and benzene (40 ml). The mixture was refluxed until no more water collected in the Dean-Stark (2 hours), cooled, benzene (30 ml) added and the organic 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 (7% to 60% EtOAc/hexanes) to give methyl 2-cyano-2-[(9Z)-6-oxaspiro[4.5]decan-9-ylidene]acetate as a colorless oil (8.93 g, 97.5%, m/z 235.1 [M+H]+ observed).

Workup

  1. customA 100 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 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 (7% to 60% EtOAc/hexanes)

Sources & evidence

ORD record
ord-d82dda1b1692478984e4a350e4353dd2
Source dataset
uspto-grants-2016_04
Patent number
US09309234B2

Reaction notes

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