Ammonia → 1-(Chloromethyl)-5-nitro-1,2-dihydro-3h-benzo[e]indole-8-carbonitrile

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Reaction Conditions

Reaction Steps

A solution of 196 (30 mg, 0.088 mmol) in HCl(g) saturated dioxane (3 mL) was stirred for 1 h. The solvent was evaporated to provide the crude amine hydrochloride (24 mg, 100%). This solid was cooled to 0° C. and treated with conc. H2SO4 (2 mL). A cooled (O OC) solution of KNO3 (9 mg, 0.088 mmol) in conc. H2SO4 (0.5 mL) was then added dropwise. After 15 min, the mixture was poured into ice water and conc. aqueous ammonia was carefully added until the pH of the mixture was 3-4. Solid KHCO3 was then carefully added until the pH of the mixture was 8. The mixture was partitioned between CH2Cl2 and water, and the aqueous layer was extracted with CH2Cl2 (×3). The combined organic extracts were washed with brine and dried. The CH2Cl2 was removed under reduced pressure and the residue was triturated with MeOH to give 1-(chloromethyl)-5-nitro-1,2-dihydro-3H-benzo[e]indole-8-carbonitrile (197) (18 mg, 72%) as red crystals: mp 231-234° C.; 1H NMR [(CD3)2SO] δ 8.54 (dd, J=1.5, 0.5 Hz, 1 H), 8.22 (dd, J=9.0, 0.4 Hz, 1H), 7.80 (s, 1H), 7.59 (dd, J=9.0, 1.6 Hz, 1H), 6.63 (d, J=1.3 Hz, 1H), 4.32-4.23 (m, 1H), 3.95 (dd, J=11.0, 3.8 Hz, 1H), 3.84 (td, J=10.3, 2.3 Hz, 1H), 3.79-3.70 (m, 2H); 13C NMR δ 151.8, 148.1, 130.6, 129.9, 126.8, 125.7, 125.0, 120.0, 119.6, 112.8, 111.4, 51.8, 47.5, 43.5. Anal. (C14H10ClN3O2) C, H, N.

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