Acetamide → HCID 67615717, compound

HRID 1598425Notes

Reaction equation

HRID 1598425 reaction equation
C[O:2][C:3]1[CH:12]=[CH:11][C:10]([O:13]C)=[C:9]2[C:4]=1[CH2:5][CH:6]([CH2:15][CH3:16])[O:7][CH2:8]2.CO.ClC1C(=O)C(C#N)=[C:23]([C:28]#[N:29])C(=O)C=1Cl.C(N)(=[O:35])C.O=[N+]([O-])[O-].[O-][N+](=O)[O-].[O-][N+](=O)[O-].[O-][N+](=O)[O-].[O-][N+](=O)[O-].[O-][N+](=O)[O-].[Ce+4].[NH4+].[NH4+].C(=O)(O)[O-].[Na+].[N+]([O-])([O-])=O.[NH4+].[Ce]>ClCCl.C(#N)C.O.CCCCC>[C:28]([NH:29][C@H:8]1[C:9]2[C:10](=[O:13])[CH:11]=[CH:12][C:3](=[O:2])[C:4]=2[CH2:5][C@H:6]([CH2:15][CH3:16])[O:7]1)(=[O:35])[CH3:23]

Participants

12

Reactant 7

HCID 178AcetamideHCID 887MethanolHCID 67752,3-Dichloro-5,6-dicyano-1,4-benzoquinoneHCID 180504Ceric ammonium nitrateHCID 516892Sodium BicarbonateHCID 18932616HCID 18932616, compoundHCID 57418452Ammonium cerium-nitrate

Product 1

HCID 67615717HCID 67615717, compoundYield 42.1%

Reagents, catalysts & solvents 4

HCID 962WaterSolventHCID 6342AcetonitrileSolventHCID 6344DichloromethaneSolvent2×HCID 8003PentaneSolvent

Conditions

Temperature
130 °C

Procedure

To a solution of 5,8-dimethoxy-3-ethyl-isochroman (1.0 g; 4.5 mmol) in dichloromethane (30 ml) at room temperature were added methanol (211 μl 5.4 mmol), 4 Å molecular sieves (2 g) and 2,3-dichloro-5,6-dicyanobenzoquinone (1.21 g; 5.4 mmol). The resulting dark mixture was stirred for 5 hours and was then quenched with saturated NaHCO3 solution. It was extracted with dichloromethane and the combined organic layers were washed with bicarbonate, brine and then dried over Na2SO4 affording after evaporation 1.0 g of crude adduct of which 300 mg (1.19 mmol assumed) were placed in a pear-shaped flask along with acetamide (70 mg; 1.19 mmol). The solid mixture was then heated to 130° C. for 30 minutes. It was then cooled to room temperature and dichloromethane was added followed by pentane yielding a precipitate (160 mg) of which 120 mg (0.43 mmol assumed) was dissolved in acetonitrile (15 ml) and treated with a solution of CAN prepared by slowly dissolving sodium bicarbonate (384 mg) in water (5 ml) containing cerium ammonium nitrate (1.46 g; 2.5 mmol). The resulting mixture was stirred at room temperature for 15 minutes and was quenched with saturated NaHCO3 solution followed by extraction with dichloromethane. The combined organic extracts were washed with brine and dried over Na2SO4 to afford the titled compound as a yellow solid (125 mg; 42% overall).

Workup

  1. customwas then quenched with saturated NaHCO3 solution
  2. extractionIt was extracted with dichloromethane
  3. washthe combined organic layers were washed with bicarbonate, brine
  4. dry with materialdried over Na2SO4 affording
  5. customafter evaporation 1.0 g of crude adduct of which 300 mg (1.19 mmol assumed)
  6. temperatureIt was then cooled to room temperature
  7. stirringThe resulting mixture was stirred at room temperature for 15 minutes
  8. customwas quenched with saturated NaHCO3 solution
  9. extractionfollowed by extraction with dichloromethane
  10. washThe combined organic extracts were washed with brine
  11. dry with materialdried over Na2SO4

Sources & evidence

ORD record
ord-b39e5839b73b427eaa3c816e9d4af54e
Source dataset
uspto-grants-1998_04
Patent number
US05736523

Reaction notes

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