Acetic Acid → ST51003188

HRID 2169298Notes

Reaction equation

HRID 2169298 reaction equation
[O:1]1[C:5]2([CH2:10][CH2:9][C:8](=O)[CH2:7][CH2:6]2)[O:4][CH2:3][CH2:2]1.[CH2:12]([O:14][C:15](=[O:19])[CH2:16][C:17]#[N:18])[CH3:13].C(O)(=O)C.C([O-])(=O)C.[NH4+]>C1(C)C=CC=CC=1>[CH2:12]([O:14][C:15](=[O:19])[C:16]([C:17]#[N:18])=[C:8]1[CH2:9][CH2:10][C:5]2([O:4][CH2:3][CH2:2][O:1]2)[CH2:6][CH2:7]1)[CH3:13]

Participants

6

Reactant 4

HCID 176Acetic AcidHCID 7764Ethyl cyanoacetateHCID 517165Ammonium AcetateHCID 5674151,4-Dioxaspiro[4.5]decan-8-one

Product 1

HCID 5114445ST51003188Yield 39.8%

Reagents, catalysts & solvents 1

HCID 1140TolueneSolvent

Conditions

Temperature
0 °C

Procedure

To a stirred solution of 1,4-dioxa-spiro[4.5]decan-8-one (261) (5.0 g, 32.01 mmol) and cyano-acetic acid ethyl ester (3.99 g, 35.31 mmol) in toluene (50 mL) were added acetic acid (0.3 mL, 5.09 mmol) and ammonium acetate (123 mg, 1.60 mmol). A Dean Stark trap and reflux condenser were attached to the reaction flask and the mixture was heated to reflux and stirred for 16 h. Thereafter, the reaction mixture was cooled to 0° C. and quenched with saturated aqueous NaHCO3 (100 ml). The aqueous layer was extracted with ethyl acetate (2×200 ml) and the combined organic layer was dried with sodium sulfate, filtered and concentrated under reduced pressure. The crude yellow oil was re-crystallized with 20% ethyl acetate in hexane to afford pure cyano-(1,4-dioxa-spiro[4.5]dec-8-ylidene)-acetic acid ethyl ester (262) (3.2 g, 39.78%) as a light yellow solid.

Workup

  1. temperatureA Dean Stark trap and reflux condenser
  2. temperaturethe mixture was heated
  3. temperatureto reflux
  4. customquenched with saturated aqueous NaHCO3 (100 ml)
  5. extractionThe aqueous layer was extracted with ethyl acetate (2×200 ml)
  6. dry with materialthe combined organic layer was dried with sodium sulfate
  7. filtrationfiltered
  8. concentrationconcentrated under reduced pressure
  9. customThe crude yellow oil was re-crystallized with 20% ethyl acetate in hexane

Sources & evidence

ORD record
ord-1640f568c59140748edf7f1d2bdbe52a
Source dataset
uspto-grants-2015_06
Patent number
US09045486B2

Reaction notes

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