Acetic Acid → tert-butyl 1-(chloromethyl)-5-nitro-1,2-dihydro-3H-benzo[e]indole-7-carbamate

HRID 2238444Notes

Reaction equation

HRID 2238444 reaction equation
[Cl:1][CH2:2][CH:3]1[C:11]2[C:10]3[CH:12]=[CH:13][C:14]([NH:16][C:17]([O:19][C:20]([CH3:23])([CH3:22])[CH3:21])=[O:18])=[CH:15][C:9]=3[C:8]([N+:24]([O-:26])=[O:25])=[CH:7][C:6]=2[N:5](C(=O)C(F)(F)F)[CH2:4]1.C([O-])([O-])=O.[Cs+].[Cs+].CC(O)=O>O1CCOCC1.O.CO>[Cl:1][CH2:2][CH:3]1[C:11]2[C:10]3[CH:12]=[CH:13][C:14]([NH:16][C:17]([O:19][C:20]([CH3:23])([CH3:21])[CH3:22])=[O:18])=[CH:15][C:9]=3[C:8]([N+:24]([O-:26])=[O:25])=[CH:7][C:6]=2[NH:5][CH2:4]1

Participants

7

Reactant 3

HCID 176Acetic AcidHCID 10796Cesium carbonateHCID 86620265tert-butyl 1-(chloromethyl)-5-nitro-3-(trifluoroacetyl)-1,2-dihydro-3H-benzo[e]indole-7-carbamate

Product 1

HCID 68696256tert-butyl 1-(chloromethyl)-5-nitro-1,2-dihydro-3H-benzo[e]indole-7-carbamateYield 94.4%

Reagents, catalysts & solvents 3

HCID 887MethanolSolventHCID 962WaterSolvent2×HCID 312751,4-DioxaneSolvent

Procedure

A suspension of 221(218 mg, 0.46 mmol) in dioxane (5 mL) was treated at room temperature with a solution of Cs2CO3 (0.33 g, 1.0 mmol) in water (1 mL) and MeOH (9 mL). The mixture was stirred at room temperature for 5 min and then treated with AcOH (0.15 mL) and diluted with water. The precipitate was collected and crystallised from CH2Cl2/hexane to give tert-butyl 1-(chloromethyl)-5-nitro-1,2-dihydro-3H-benzo[e]indole-7-carbamate (222) (164 mg, 94%) as a red solid: mp 162-163° C. (dec.); 1H NMR [(CD3)2SO] δ 9.57 (s, 1H), 8.46 (d, J=1.7 Hz, 1H), 7.81 (d, J=9.1 Hz, 1H), 7.65-7.57 (m, 2H), 6.09 (d, J=2.1 Hz, 1H), 4.19-4.10 (m, 1H), 3.88 (dd, J=10.9, 3.7 Hz, 1H), 3.81-3.63 (m, 3H), 1.50 (s, 9H). Anal. (C18H20ClN3O4) C, H, N.

Workup

  1. customThe precipitate was collected
  2. customcrystallised from CH2Cl2/hexane

Sources & evidence

ORD record
ord-4b4133e366dd4f38b519f5e16d55d378
Source dataset
uspto-grants-2010_05
Patent number
US07718688B2

Reaction notes

Loading…