Pyridine → 1,1-di(methoxycarbonyl)-5-nitro-1,2-dihydro-3H-benz[e]indole-2one

HRID 366801Notes

Reaction equation

HRID 366801 reaction equation
[CH3:1][O:2][C:3]([CH:5]([C:22]([O:24][CH3:25])=[O:23])[C:6]1[C:15]2[C:10](=[CH:11][CH:12]=[CH:13][CH:14]=2)[C:9]([N+:16]([O-:18])=[O:17])=[CH:8][C:7]=1C(O)=O)=[O:4].[N-]=[N+]=[N-].[Na+].[N:30]1[CH:35]=CC=CC=1.[Cl-].C[N+](C)=CS(Cl)(=O)=[O:41]>C1(C)C=CC=CC=1>[CH3:1][O:2][C:3]([C:5]1([C:22]([O:24][CH3:25])=[O:23])[C:6]2[C:15]3[CH:14]=[CH:13][CH:12]=[CH:11][C:10]=3[C:9]([N+:16]([O-:18])=[O:17])=[CH:8][C:7]=2[NH:30][C:35]1=[O:41])=[O:4]

Participants

6

Reactant 4

HCID 1049PyridineHCID 33557Sodium AzideHCID 105215641-[Di(methoxycarbonyl)-methyl]-4-nitronaphthalene-2-carboxylic acidHCID 15710081(Chlorosulfonyl)-N,N-dimethylmethaniminium chloride

Product 1

HCID 104975971,1-di(methoxycarbonyl)-5-nitro-1,2-dihydro-3H-benz[e]indole-2oneYield 81%

Reagents, catalysts & solvents 1

HCID 1140TolueneSolvent

Conditions

Temperature
-5 °C

Procedure

A stirred suspension of 6 (7.00 g, 20.16 mmol) and powdered NaN3 (3.28 g, 50.44 mmol) in CH2'Cl2 (100 mL) was treated with pyridine (3.99 g, 50.44 mmol), then cooled to -5° C. and treated in one portion with N,N-dimethyl(chlorosulfonyl)methaniminium chloride [SOCl2 /DMF adduct] (4.26 g, 22.18 mmol). After stirring at 20° C. for 2 h, the mixture was washed twice with water, dried (Na2SO4) and filtered through a short column of silica gel, eluting with further CH2Cl2 (400 mL). Removal of the solvent under reduced pressure below 30° C. gave the crude carbonyl azide (7), which was immediately heated with stirring in dry toluene (65 mL) under reflux for 8 min. The mixture was cooled to 0° C. to complete precipitation of the product, which was collected and washed with toluene. This was stirred as a suspension in CH2Cl2 (25 mL) for 10 min at 20° C., diluted with iPr2O, and the resulting solid collected to give 1,1-di(methoxycarbonyl)-5-nitro-1,2-dihydro-3H-benz[e]indole-2one (8) (5.60 g, 81%). A sample crystallised from CH2Cl2 had mp 218-222° C. (dec.). 1H NMR [CD3)2SO] δ 11.59 (s, 1H, NH), 8.21 (d, J=8.7 Hz, 1H, H-7), 7.95 (s, 1H, H-9), 7.87 (d, J=8.5 Hz, 1H, H-4), 7.74 (t, J=7.6 Hz, 1H, H-6), 7.65 (t, J=7.7 Hz, 1H, H-5), 3.72 (s, 6H, 2×CO2CH3). Anal. Calculated for C16H12N2O7.1.5 H2O: C, 51.8; H, 4.1; N, 7.5. Found: C, 52.1; H, 3.1; N, 7.8%.

Workup

  1. washthe mixture was washed twice with water
  2. dry with materialdried (Na2SO4)
  3. filtrationfiltered through a short column of silica gel
  4. washeluting with further CH2Cl2 (400 mL)
  5. customRemoval of the solvent under reduced pressure below 30° C.
  6. customgave the crude carbonyl azide (7), which
  7. temperaturewas immediately heated
  8. temperatureunder reflux for 8 min
  9. temperatureThe mixture was cooled to 0° C.
  10. customprecipitation of the product, which
  11. customwas collected
  12. washwashed with toluene
  13. stirringThis was stirred as a suspension in CH2Cl2 (25 mL) for 10 min at 20° C.
  14. additiondiluted with iPr2O
  15. customthe resulting solid collected

Sources & evidence

ORD record
ord-3dc24a8b7d0c4db4b71f3ac840345025
Source dataset
uspto-grants-2000_10
Patent number
US06130237

Reaction notes

Loading…