Tributylstannane → tert-butyl 1-(chloromethyl)-7-cyano-1,2-dihydro-3H-benzo[e]indole-3-carboxylate

HRID 2238395Notes

Reaction equation

HRID 2238395 reaction equation
Br[C:2]1[C:11]2[C:6](=[CH:7][C:8]([C:12]#[N:13])=[CH:9][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]=[CH:9][C:8]([C:12]#[N:13])=[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 75066177Tert-butyl 1-bromo-6-cyano-2-naphthyl(3-chloro-2-propenyl)carbamate

Product 1

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

Reagents, catalysts & solvents 1

HCID 241BenzeneSolvent

Procedure

A solution of 142 (6.78 g, 16.1 mmol) in dry benzene (80 mL) was treated with Bu3SnH (4.33 mL, 16.1 mmol), followed by AIBN (0.3 g, 1.8 mmol). The mixture was stirred at reflux under N2 for 2 h, then concentrated under reduced pressure, and the residue was chromatographed on silica gel. Elution with CH2Cl2 gave an oil that was triturated with iPr2O, to provide 143 contaminated with tert-butyl 7-cyano-1-methyl-1,2-dihydro-3H-benzo[e]indole-3-carboxylate. Two recrystallizations from CH2ClrPr2O gave pure tert-butyl 1-(chloromethyl)-7-cyano-1,2-dihydro-3H-benzo[e]indole-3-carboxylate (143) (4.49 g, 81%): mp 171-172° C.; 1H MR [(CD3)2SO] δ 8.55 (d, J=1.4 Hz, 1H), 8.18 (v br, 1H), 8.07 (d, J=8.7 Hz, 1H), 8.01 (d, J=8.9 Hz, 1H), 7.75 (dd, J=8.7, 1.7 Hz, 1 H), 4.34-4.25 (m, 1H), 4.21 (t, J=10.5 Hz, 1H), 4.09 (dd, J=11.3, 2.8 Hz, 1H), 4.03 (dd, J=11.1, 3.1 Hz, 1H), 3.93 (dd, J=11.1, 6.7 Hz, 1H), 1.55 (s, 9H). Anal. (C19H19ClN2O2.¼H2O) C, H, N.

Workup

  1. temperatureat reflux under N2 for 2 h
  2. concentrationconcentrated under reduced pressure
  3. customthe residue was chromatographed on silica gel
  4. washElution with CH2Cl2
  5. customgave an oil that
  6. customwas triturated with iPr2O

Sources & evidence

ORD record
ord-3febfa2b80324bdf8bb9dbb325385fc4
Source dataset
uspto-grants-2010_05
Patent number
US07718688B2

Reaction notes

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