Ethanol → HCID 9817050, compound

HRID 1591419Notes

Reaction equation

HRID 1591419 reaction equation
[Cl:1][C:2]1[C:7]([N+:8]([O-])=O)=[C:6]([Cl:11])[N:5]=[C:4]([NH:12][C:13](=[O:17])[CH:14]([CH3:16])[CH3:15])[N:3]=1.C[CH2:19][OH:20]>[Ni]>[Cl:1][C:2]1[C:7]([NH:8][CH:19]=[O:20])=[C:6]([Cl:11])[N:5]=[C:4]([NH:12][C:13](=[O:17])[CH:14]([CH3:16])[CH3:15])[N:3]=1

Participants

4

Reactant 2

HCID 702EthanolHCID 9925643HCID 9925643, compound

Product 1

HCID 9817050HCID 9817050, compoundYield 73%

Reagents, catalysts & solvents 1

HCID 935NickelCatalyst

Procedure

The title compound of Example 24 (6.77 g, 24.26 mmol) was placed in a Parr bottle containing 220 ml absolute EtOH and 10.0 g (wet) Raney nickel catalyst that had been previously shaken under hydrogen (40 psi) for 10 minutes. The mixture was shaken under hydrogen (40 psi) for an hour, filtered over celite, and the filtrate was concentrated to a yellow-white solid that was dried under vacuum overnight. This solid was stirred in 1,2-dichloroethane (250 ml) at 0° C. Acetic anhydride (30 ml) was added, followed by formic acid (30 ml), dropwise under nitrogen. The resulting mixture was stirred at room temperature for 2 hours, concentrated to half the original volume; and azeotroped with toluene to remove residual formic/acetic acid. The crude solid was triturated with methanol to give the title compound (4.92 g, 73%) as an off-white solid; m.p. 206°-209° C. (dec); 'H-NMR (DMSO-d6) δ 1.08 (d, J=6.8 Hz, 6.0 (CH3)2CH), 2.74 (m, J=6.8 Hz, 1.0 (CH3)2CH), 8.18 (d, J=10.3 Hz) and 10.26 (br s) [total 1.0, NHCHO from two conformers], 11.17 (br s, 1.0).

Workup

  1. stirringThe mixture was shaken under hydrogen (40 psi) for an hour
  2. filtrationfiltered over celite
  3. concentrationthe filtrate was concentrated to a yellow-white solid
  4. customthat was dried under vacuum overnight
  5. stirringThis solid was stirred in 1,2-dichloroethane (250 ml) at 0° C
  6. additionAcetic anhydride (30 ml) was added
  7. stirringThe resulting mixture was stirred at room temperature for 2 hours
  8. concentrationconcentrated to half the original volume
  9. customand azeotroped with toluene
  10. customto remove residual formic/acetic acid
  11. customThe crude solid was triturated with methanol

Sources & evidence

ORD record
ord-0952e5611be54cc6af7e66133196cf43
Source dataset
uspto-grants-1993_04
Patent number
US05206435

Reaction notes

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