Ammonia → methyl 1-(chloromethyl)-9-nitro-1,2-dihydro-3H-benzo[e]indole-7-carboxylate

HRID 2238402Notes

Reaction equation

C(OC([N:8]1[C:16]2[CH:15]=[CH:14][C:13]3[CH:17]=[C:18]([C:21]([O:23][CH3:24])=[O:22])[CH:19]=[CH:20][C:12]=3[C:11]=2[CH:10]([CH2:25][Cl:26])[CH2:9]1)=O)(C)(C)C.[N+:27]([O-])([O-:29])=[O:28].[K+].N>OS(O)(=O)=O>[Cl:26][CH2:25][CH:10]1[C:11]2[C:12]3[C:20]([N+:27]([O-:29])=[O:28])=[CH:19][C:18]([C:21]([O:23][CH3:24])=[O:22])=[CH:17][C:13]=3[CH:14]=[CH:15][C:16]=2[NH:8][CH2:9]1

Participants

Conditions

Temperature: -5 °C

Procedure

Powdered 150 (900 mg, 2.39 mmol) was added to stirred conc. H2SO4 (6 mL) at 0° C. and the mixture was warned to room temperature for 15 nm. The resulting solution was cooled to −5° C. and treated dropwise with a solution of KNO3 (266 mg, 2.63 mmol) in conc. H2SO4 (1.5 mL). The mixture was stirred at −5° C. for a further 5 min, then poured into ice/water and neutralized with dilute aqueous NH3. The resulting solid was chromatographed on silica gel, eluting with CH2Cl2 to give crude methyl 1-(chloromethyl)-9-nitro-1,2-dihydro-3H-benzo[e]indole-7-carboxylate (151) (102 mg, 13%) as an orange-brown solid; 1H NMR [(CD3)2SO] δ 8.66 (d, J=1.7 Hz, 1H), 8.30 (d, J=1.7 Hz, 1H), 8.08 (d, J=8.8 Hz, 1H), 7.25 (s, 1H), 7.18 (d, J=8.8 Hz, 1H), δ 3.92-3.83 (m, 4H), 3.74-3.67 (m, 1H), 3.63 (dd, J=10.6, 2.3 Hz, 1H), 3.39-3.28 (m, 2 H).

Workup

customwas warned to room temperature for 15 nm
customThe resulting solid was chromatographed on silica gel
washeluting with CH2Cl2

Sources & evidence

ORD record: ord-b0a0d4c48fb045eaa59bd2d471ff5fad
Source dataset: uspto-grants-2010_05
DOI: 10.6084/m9.figshare.5104873.v1
Patent number: US07718688B2

Reaction notes

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