Trifluoroacetic acid → 3-(tert-butyloxycarbonyl)-1-methoxycarbonyl-5-nitro-1,2-dihydro-3H-benz[e]indole

HRID 366802Notes

Reaction equation

HRID 366802 reaction equation
C[O-].[Na+].[C:4]([O:8][C:9]([N:11]1[C:19]2[CH:18]=[C:17]([N+:20]([O-:22])=[O:21])[C:16]3[CH:23]=[CH:24][CH:25]=[CH:26][C:15]=3[C:14]=2[C:13](C(OC)=O)([C:27]([O:29][CH3:30])=[O:28])[CH2:12]1)=[O:10])([CH3:7])([CH3:6])[CH3:5].FC(F)(F)C(O)=O>CO.C1COCC1.[Na+].[Cl-]>[C:4]([O:8][C:9]([N:11]1[C:19]2[CH:18]=[C:17]([N+:20]([O-:22])=[O:21])[C:16]3[CH:23]=[CH:24][CH:25]=[CH:26][C:15]=3[C:14]=2[CH:13]([C:27]([O:29][CH3:30])=[O:28])[CH2:12]1)=[O:10])([CH3:7])([CH3:6])[CH3:5]

Participants

7

Reactant 3

HCID 6422Trifluoroacetic acidHCID 105266213-(tert-butyloxycarbonyl)-1,1-di(methoxycarbonyl)-5-nitro-1,2-dihydro-3H-benz[e]indoleHCID 10942334Sodium Methoxide

Product 1

HCID 105713133-(tert-butyloxycarbonyl)-1-methoxycarbonyl-5-nitro-1,2-dihydro-3H-benz[e]indoleYield 98.4%

Reagents, catalysts & solvents 3

HCID 887MethanolSolventHCID 5234Sodium ChlorideSolventHCID 8028TetrahydrofuranSolvent

Procedure

NaOMe (5.61 mL of a 0.62 M solution in MeOH, 3.48 mmol) was added dropwise to a stirred solution of 10 (1.00 g, 2.32 mmol) in THF (20 mL) at 10° C. After 15 min at 20° C., trifluoroacetic acid (0.29 mL, 3.8 mmol) was added in one portion, causing dissipation of the deep purple colour of the solution. The reaction was diluted with saturated NaCl, extracted with CH2Cl2 and the extract was washed twice with water and dried (Na2SO4). The CH2Cl2 solution was filtered through a short column of silica gel, eluting with additional CH2Cl2, and the solvent was evaporated under reduced pressure below 30° C. to give crude 3-(tert-butyloxycarbonyl)-1-methoxycarbonyl-5-nitro-1,2-dihydro-3H-benz[e]indole (11) (0.85 g, 98%), which was used without further purification. 1H NMR (CDCl3) δ8.89 (br s, 1 H, H-9), 8.38 (br s, 1 H, H-7), 7.87 (d, J=8.3 Hz, 1 H, H-4), 7.63-7.51 (m, 2 H, H-5,6), 4.61 (dd, J=10.5, 3.9 Hz, 1 H, NCH2CH), 4.50 (br s, 1 H, NCH2CH), 4.32 (t, J=11.1 Hz, 1 H, HCH2CH), 3.72 (s, 3 H, CO2CH3), 1.61 (s, 9 H, C(CH3)3).

Workup

  1. extractionextracted with CH2Cl2
  2. washthe extract was washed twice with water
  3. dry with materialdried (Na2SO4)
  4. filtrationThe CH2Cl2 solution was filtered through a short column of silica gel
  5. washeluting with additional CH2Cl2
  6. customthe solvent was evaporated under reduced pressure below 30° C.

Sources & evidence

ORD record
ord-1c8d04ed830c4d60b1b2d555ad497fdb
Source dataset
uspto-grants-2000_10
Patent number
US06130237

Reaction notes

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