Tributylstannane → tert-butyl 1-(chloromethyl)-8-cyano-1,2-dihydro-3H-benzo[e]indole-3-carboxylate

HRID 2238425Notes

Reaction equation

HRID 2238425 reaction equation
Br[C:2]1[C:11]2[C:6](=[CH:7][CH:8]=[C:9]([C:12]#[N:13])[CH:10]=2)[CH:5]=[CH:4][C:3]=1[N:14]([CH2:22][CH:23]=[CH:24][Cl:25])[C:15](=[O:21])[O:16][C:17]([CH3:20])([CH3:19])[CH3:18].CCCC[SnH](CCCC)CCCC.CC(N=NC(C#N)(C)C)(C#N)C>C1C=CC=CC=1>[Cl:25][CH2:24][CH:23]1[C:2]2[C:11]3[CH:10]=[C:9]([C:12]#[N:13])[CH:8]=[CH:7][C:6]=3[CH:5]=[CH:4][C:3]=2[N:14]([C:15]([O:16][C:17]([CH3:20])([CH3:19])[CH3:18])=[O:21])[CH2:22]1

Participants

5

Reactant 3

HCID 5948TributylstannaneHCID 6547AzobisisobutyronitrileHCID 75066243Tert-butyl 1-bromo-7-cyano-2-naphthyl(3-chloro-2-propen-1-yl)carbamate

Product 1

HCID 44550496tert-butyl 1-(chloromethyl)-8-cyano-1,2-dihydro-3H-benzo[e]indole-3-carboxylateYield 92%

Reagents, catalysts & solvents 1

HCID 241BenzeneSolvent

Procedure

A mixture of 195 (3.00 g, 7.13 mmol), Bu3SnH (2.49 g, 8.55 mmol) and AIBN (120 mg, 0.71 mmol) in benzene (20 mL) was heated under reflux for 1.5 h. The benzene was removed under reduced pressure and the residue was triturated with pentane (×4) and recrystallised (MeOH) to give tert-butyl 1-(chloromethyl)-8-cyano-1,2-dihydro-3H-benzo[e]indole-3-carboxylate (196) (2.24 g, 92%) as colorless needles: mp 138-140° C.; 1H NMR (CDCl3) δ 8.35 (br s, 1H), 8.09 (s, 1H), 7.90 (d, J=8.5 Hz, 1H), 7.82 (d, J=9.0 Hz, 1H), 7.48 (dd, J=8.5, 1.5 Hz, 1H), 430 (br d, J=11.2 Hz, 1H), 4.18 (dd, J=11.8, 8.7 Hz, 1H), 4.50 (tt, J=9.3, 3.0 Hz, 1H), 3.87 (dd, J=−11.3, 3.3 Hz, 1H), 3.53 (dd, J=11.2, 9.6 Hz, 1H), 1.61 (s, 9 M); 13C NMR δ 152.3, 142.9, 131.2, 130.2, 130.0, 128.9, 128.2, 124.2, 123.3, 119.2, 118.8, 110.5, 81.8, 52.8, 462, 41.5, 28.4. Anal. (C19H19ClN2O2) C, H, N.

Workup

  1. temperaturewas heated
  2. temperatureunder reflux for 1.5 h
  3. customThe benzene was removed under reduced pressure
  4. customthe residue was triturated with pentane (×4)
  5. customrecrystallised (MeOH)

Sources & evidence

ORD record
ord-e4f62ff26db84e8399ef8a911bf5e960
Source dataset
uspto-grants-2010_05
Patent number
US07718688B2

Reaction notes

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