Ammonia → HCID 4060849, compound

HRID 525498Notes

Reaction equation

HRID 525498 reaction equation
N.C[O:3][C:4]1[CH:9]=[CH:8][C:7]([Si:10]([CH3:13])([CH3:12])[CH3:11])=[CH:6][CH:5]=1.[Na].C(O)(=O)C(O)=O>CCOCC.O.CCO>[CH3:11][Si:10]([CH3:13])([CH3:12])[CH:7]1[CH2:8][CH2:9][C:4](=[O:3])[CH2:5][CH2:6]1

Participants

8

Reactant 4

HCID 222Ammonia2×HCID 971Oxalic AcidHCID 136689Silane, (4-methoxyphenyl)trimethyl-HCID 5360545Sodium

Product 1

HCID 4060849HCID 4060849, compoundYield 82.2%

Reagents, catalysts & solvents 3

HCID 702EthanolSolvent2×HCID 962WaterSolvent2×HCID 3283Diethyl EtherSolvent

Procedure

Ammonia (100 mL) was condensed at −78° C. (4-methoxyphenyl)trimethylsilane (18.0 g, 0.1 mol, 1.0 eq) in anhydrous Et2O (110 mL) was added followed by EtOH (80 mL) and sodium (23.0 g, 1.0 mol, 10.0 eq) portionwise at −33° C. Additional EtOH (50 mL) was added and ammonia was allowed to evaporated over 16 h. Then water (250 mL) was added to the residue and the mixture was extracted with Et2O (250 mL×3). The combined organic extracts were dried over anhydrous Na2SO4, filtered and concentrated in vacuo. The crude product was dissolved in EtOH (20 mL) and H2O (20 mL) and oxalic acid (2.71 g, 0.03 mol, 0.3 eq) was then added. The resulting colorless solution was stirred at room temperature for 2 h. Water (100 mL) was then added and the mixture was extracted with Et2O (100 mL×3). The combined organic extracts were washed with brine, dried over anhydrous Na2SO4, filtered and concentrated in vacuo. The residue was purified by column chromatography on silica gel (petroleum ether/EtOAc=10:1) to furnish 4-(trimethylsilyl)cyclohexanone as a light yellow oil (14.0 g, 72% yield). 1H NMR (300 MHz, CDCl3) δ: 2.44-2.39 (m, 2H), 2.33-2.22 (m, 2H), 2.11-2.05 (m, 2H), 1.53-1.47 (m, 2H), 0.96-0.87 (m, 1H), 0.00 (s, 9H).

Workup

  1. additionwas added
  2. customto evaporated over 16 h
  3. additionThen water (250 mL) was added to the residue
  4. extractionthe mixture was extracted with Et2O (250 mL×3)
  5. dry with materialThe combined organic extracts were dried over anhydrous Na2SO4
  6. filtrationfiltered
  7. concentrationconcentrated in vacuo
  8. dissolutionThe crude product was dissolved in EtOH (20 mL)
  9. extractionthe mixture was extracted with Et2O (100 mL×3)
  10. washThe combined organic extracts were washed with brine
  11. dry with materialdried over anhydrous Na2SO4
  12. filtrationfiltered
  13. concentrationconcentrated in vacuo
  14. customThe residue was purified by column chromatography on silica gel (petroleum ether/EtOAc=10:1)

Sources & evidence

ORD record
ord-a2798cff34b749bda062688b732aa8ae
Source dataset
uspto-grants-2016_05
Patent number
US09340527B2

Reaction notes

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