Ammonia → (2,2-dimethyl-2H-chromen-6-yl)methanamine

HRID 2041165Notes

Reaction equation

HRID 2041165 reaction equation
[CH3:1][C:2]1([CH3:14])[CH:11]=[CH:10][C:9]2[C:4](=[CH:5][CH:6]=[C:7]([C:12]#[N:13])[CH:8]=2)[O:3]1.C(O)C.N>CO.[Ni]>[NH2:13][CH2:12][C:7]1[CH:8]=[C:9]2[C:4](=[CH:5][CH:6]=1)[O:3][C:2]([CH3:14])([CH3:1])[CH:11]=[CH:10]2

Participants

6

Reactant 3

HCID 222AmmoniaHCID 702EthanolHCID 27790742,2-dimethyl-2H-1-benzopyran-6-carbonitrile

Product 1

HCID 55255597(2,2-dimethyl-2H-chromen-6-yl)methanamineYield 97.9%

Reagents, catalysts & solvents 2

HCID 935NickelCatalystHCID 887MethanolSolvent

Conditions

Temperature
60 °C

Procedure

Add 2,2-dimethyl-2H-chromene-6-carbonitrile (1.5 g, 8.1 mmol) and ethanol wet Raney® activated nickel (0.4 g) to a Parr pressure vessel. Immediately add 7N ammonia in methanol (170 mL) and seal the vessel. Purge the reaction vessel with nitrogen, pressurize the reaction mixture with hydrogen (3400 KPa), seal the vessel, agitate the reaction and heat to 60° C. for 20 h. Turn off the heat and allow the reaction mixture to cool to ambient temperature. Vent the excess hydrogen from the vessel and purge the vessel with nitrogen. Filter the reaction mixture to remove the Raney® nickel. Purify by chromatography on silica gel eluting with DCM/2M ammonia in methanol (9:1) to obtain the title compound (1.5 g, 97%). MS (ES+) m/z: 175 (M+H—NH3)+.

Workup

  1. customPurge the reaction vessel with nitrogen
  2. customseal the vessel
  3. customthe reaction
  4. temperatureheat
  5. temperatureto cool to ambient temperature
  6. customVent the excess hydrogen from the vessel and purge the vessel with nitrogen
  7. filtrationFilter the reaction mixture
  8. customto remove the Raney® nickel
  9. customPurify by chromatography on silica gel eluting with DCM/2M ammonia in methanol (9:1)

Sources & evidence

ORD record
ord-dbd374736519461496e6c0f2567f3eb6
Source dataset
uspto-grants-2013_11
Patent number
US08580780B2

Reaction notes

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