Sodium Hydroxide → 1-Acetyl-8-nitro-2,3,5,6-tetrahydro-1H-benzo[b][1,5]diazocin-4-one

HRID 1687568Notes

Reaction equation

HRID 1687568 reaction equation
[C:1]([N:4]1[CH2:11][CH2:10][C:9](=[O:12])[NH:8][CH2:7][C:6]2[CH:13]=[CH:14][CH:15]=[CH:16][C:5]1=2)(=[O:3])[CH3:2].[OH-].[Na+].[N+:19]([O-])([OH:21])=[O:20].OS(O)(=O)=O>>[C:1]([N:4]1[CH2:11][CH2:10][C:9](=[O:12])[NH:8][CH2:7][C:6]2[CH:13]=[C:14]([N+:19]([O-:21])=[O:20])[CH:15]=[CH:16][C:5]1=2)(=[O:3])[CH3:2]

Participants

4

Reactant 3

HCID 14798Sodium HydroxideHCID 672641101-Acetyl-2,3,5,6-tetrahydro-1H-benzo[b][1,5]diazocin-4-oneHCID 71777668Sulfuric acid, mixt. with nitric acid

Product 1

HCID 672645601-Acetyl-8-nitro-2,3,5,6-tetrahydro-1H-benzo[b][1,5]diazocin-4-one

Conditions

Temperature
0 °C

Procedure

1-Acetyl-2,3,5,6-tetrahydro-1H-benzo[b][1,5]diazocin-4-one (1.05 g, 4.82 mmol) was added to a 1/1 mixture of HNO3/H2SO4 (20 ml) at 0° C. The resulting solution was stirred at 0° C. for 3 h and allowed to warm to rt over 16 h. The reaction mixture was poured onto ice and neutralized with NaOH. The resulting ppt was filtered and washed with H2O to afford title compound as a pale orange solid. (600 mg, 47%). mp 253-256° C.; LCMS: m/z=264.25 (M+H+), HPLC (95% purity); 1H NMR (400 MHz, DMSO-d6) δ 8.31 (s, 1H), 8.24 (d, J=8.8 Hz, 1H), 7.79 (m, 1H), 7.69 (d, J=8.6 Hz, 1H). 4.65 (m, 1H), 4.38 (m, 1H), 4.11 (m, 1H), 2.96 (m, 1H), 2.61 (m, 1H), 2.38 (m, 1H), 1.73 (s, 3H).

Workup

  1. temperatureto warm to rt over 16 h
  2. filtrationThe resulting ppt was filtered
  3. washwashed with H2O

Sources & evidence

ORD record
ord-e903579484004964967cb8ee4bf3640f
Source dataset
uspto-grants-2012_04
Patent number
US08148391B2

Reaction notes

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