Ammonia → 1-(chloromethyl)-7-cyano-5-nitro-1,2-dihydro-3H-benzo[e]indole

HRID 2238396Notes

Reaction equation

HRID 2238396 reaction equation
[Cl:1][CH2:2][CH:3]1[C:11]2[C:10]3[CH:12]=[CH:13][C:14]([C:16]#[N:17])=[CH:15][C:9]=3[CH:8]=[CH:7][C:6]=2[N:5](C(OC(C)(C)C)=O)[CH2:4]1.[N+:25]([O-])([O-:27])=[O:26].[K+].N>OS(O)(=O)=O>[Cl:1][CH2:2][CH:3]1[C:11]2[C:10]3[CH:12]=[CH:13][C:14]([C:16]#[N:17])=[CH:15][C:9]=3[C:8]([N+:25]([O-:27])=[O:26])=[CH:7][C:6]=2[NH:5][CH2:4]1

Participants

5

Reactant 3

HCID 222AmmoniaHCID 24434Potassium NitrateHCID 44550490tert-butyl 1-(chloromethyl)-7-cyano-1,2-dihydro-3H-benzo[e]indole-3-carboxylate

Product 1

HCID 445494011-(chloromethyl)-7-cyano-5-nitro-1,2-dihydro-3H-benzo[e]indoleYield 62.6%

Reagents, catalysts & solvents 1

HCID 1118Sulfuric AcidSolvent2×

Procedure

Powdered carbamate 143 (1.00 g, 2.9 mmol) was added portionwise to stirred conc. H2SO4 (10 mL) at 0° C., and the mixture was warmed to room temperature for 10 min. The resulting solution was cooled to −5° C. and treated dropwise with a solution of KNO3 (324 mg, 3.2 mmol) in cone. H2SO4 (2 mL). After siting for a flirter 5 min at 0° C., the mixture was poured into ice/water and neutralized with dilute aqueous NH3. The resulting solid was purified by chromatography on silica gel, eluting with CH2Cl2, followed by recrystallization from CH2Cl2, then EtOAc, to give 1-(chloromethyl)-7-cyano-5-nitro-1,2-dihydro-3H-benzo[e]indole (144) (522 mg, 62%) as a red solid: mp 237-238° C.; 1H NMR [(CD3)2SO] δ 8.55 (d, J=1.4 Hz, 1H), 7.98 (d, J=8.8 Hz, 1H), 7.77 (s, 1H), 7.74 (dd, J=8.8, 1.5 Hz, 1H), 6.87 (s, 1H), 4.29-4.21 (m, 1H), 3.94-3.85 (m, 2H), 3.80 (dd, J=11.1, 8.1 Hz, 1H), 3.75 (dd, J=10.6, 3.1 Hz, 1H). Anal. (C14H10ClN3O2) C, H, N, Cl.

Workup

  1. temperatureThe resulting solution was cooled to −5° C.
  2. customThe resulting solid was purified by chromatography on silica gel
  3. washeluting with CH2Cl2
  4. customfollowed by recrystallization from CH2Cl2

Sources & evidence

ORD record
ord-16733de696af4bf68a33aece65ac4956
Source dataset
uspto-grants-2010_05
Patent number
US07718688B2

Reaction notes

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