Nitric Acid → 1-(chloromethyl)-3-(trifluoroacetyl)-7-nitro-1,2-dihydro-3H-benzo[e]indole

HRID 2238387Notes

Reaction equation

HRID 2238387 reaction equation
[Cl:1][CH2:2][CH:3]1[C:11]2[C:10]3[CH:12]=[CH:13][CH:14]=[CH:15][C:9]=3[CH:8]=[CH:7][C:6]=2[N:5]([C:16](=[O:21])[C:17]([F:20])([F:19])[F:18])[CH2:4]1.[N+:22]([O-])([OH:24])=[O:23]>C(Cl)Cl>[Cl:1][CH2:2][CH:3]1[C:11]2[C:10]3[CH:12]=[CH:13][C:14]([N+:22]([O-:24])=[O:23])=[CH:15][C:9]=3[CH:8]=[CH:7][C:6]=2[N:5]([C:16](=[O:21])[C:17]([F:20])([F:18])[F:19])[CH2:4]1

Participants

4

Reactant 2

HCID 944Nitric AcidHCID 445491451-(chloromethyl)-3-(trifluoroacetyl)-1,2-dihydro-3H-benz[e]indole

Product 1

HCID 445491461-(chloromethyl)-3-(trifluoroacetyl)-7-nitro-1,2-dihydro-3H-benzo[e]indoleYield 39%

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent2×

Procedure

A stirred solution of 108 (5.24 g, 16.7 mmol) in dry CH2Cl2 (70 mL) was treated dropwise at 10° C. with fuming HNO3 (2.0 mL, 48 mmol) and then warmed to room temperature for 5 min. The mixture was diluted with CH2Cl2 (100 mL) and the resulting solution was washed with water, dried, filtered through a column of silica gel, then concentrated to 25 mL and diluted with EtOAc (25 mL). Following refrigeration the precipitate was collected and washed with EtOAc to give 1-(chloromethyl)-3-(trifluoroacetyl)-7-nitro-1,2-dihydro-3H-benzo[e]indole (131) (2.31 g, 39%) as a pale yellow solid: mp (CH2Cl2/iPr2O) 213-214° C.; 1H NMR [(CD3)2SO] δ 9.06 (s, 1H), 8.48 (d, J=9.0 Hz, 1H), 8.36 (d, J=9.1 Hz, 1H), 8.33-8.25 (m, 2H) 4.67-4.51 (m, 2H), 4.46 (br d, J=10.6 Hz, 1H), 4.17 (dd, J=11.3, 3.0 Hz, 1H), 4.07 (dd, J=11.3, 5.5 Hz, 1H). Anal. (C15H10ClF3N2O3) C, H, N.

Workup

  1. washthe resulting solution was washed with water
  2. customdried
  3. filtrationfiltered through a column of silica gel
  4. concentrationconcentrated to 25 mL
  5. additiondiluted with EtOAc (25 mL)
  6. customwas collected
  7. washwashed with EtOAc

Sources & evidence

ORD record
ord-a106727c6cb148f98e71777eea184904
Source dataset
uspto-grants-2010_05
Patent number
US07718688B2

Reaction notes

Loading…