Acetic Acid → HCID 86176832, compound

HRID 522240Notes

Reaction equation

HRID 522240 reaction equation
O1[C:5]2([CH2:10][CH2:9][C:8](=[O:11])[CH2:7][CH2:6]2)OCC1.[C:12]([CH2:14][C:15]([O:17][C:18]([CH3:21])([CH3:20])[CH3:19])=[O:16])#[N:13].C([O-])(=O)C.[NH4+].C(O)(=O)C>C1(C)C=CC=CC=1.O>[C:12]([C:14](=[C:5]1[CH2:6][CH2:7][C:8](=[O:11])[CH2:9][CH2:10]1)[C:15]([O:17][C:18]([CH3:21])([CH3:20])[CH3:19])=[O:16])#[N:13]

Participants

7

Reactant 4

HCID 176Acetic Acid2×HCID 70693tert-Butyl cyanoacetateHCID 517165Ammonium AcetateHCID 5674151,4-Dioxaspiro[4.5]decan-8-one

Product 1

HCID 86176832HCID 86176832, compound

Reagents, catalysts & solvents 2

HCID 962WaterSolvent2×HCID 1140TolueneSolvent

Procedure

A solution of 1,4-dioxaspiro[4.5]decan-8-one (5 g, 32.0 mmol), tert-butyl 2-cyanoacetate (4.97 g, 35.2 mmol), ammonium acetate (0.2 g) and acetic acid (1.0 mL) in toluene (75 ml) was refluxed using Dean-Stark water separator to isolate water formed for 16 hours. After cooling, the reaction mixture was washed twice with water, dried over Na2SO4, filtered, and concentrated in vacuo. The crude material (4.18 g, 14.96 mmol) was treated with acetic acid (80% in water, 42.8 mL, 599 mmol) at 65° C. overnight. The reaction mixture was concentrated in vacuo and the residue was purified by flash chromatography on Analogix IntelliFlash280 eluting with 5 to 100% ethyl acetate/hexanes to give the title compound. 1H NMR (501 MHz, CDCl3) δ 1.54 (s, 9H), 2.49-2.62 (m, 4H), 3.05-3.16 (m, 2H), 3.37 (t, J=7.0 Hz, 2H).

Workup

  1. customformed for 16 hours
  2. temperatureAfter cooling
  3. washthe reaction mixture was washed twice with water
  4. dry with materialdried over Na2SO4
  5. filtrationfiltered
  6. concentrationconcentrated in vacuo
  7. concentrationThe reaction mixture was concentrated in vacuo
  8. customthe residue was purified by flash chromatography on Analogix IntelliFlash280
  9. washeluting with 5 to 100% ethyl acetate/hexanes

Sources & evidence

ORD record
ord-130cf259fa8a41a3a4e1948cdbf2bc36
Source dataset
uspto-grants-2016_05
Patent number
US09328112B2

Reaction notes

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