Stannane, tributyl(4-nitrophenyl)- → 8-Chloro-3-methoxy-4-(4-nitrophenyl)-2,5-dioxo-2,5-dihydro-1H-benz[b]azepine

HRID 2256995Notes

Reaction equation

HRID 2256995 reaction equation
[Cl:1][C:2]1[CH:3]=[CH:4][C:5]2[C:11](=[O:12])[C:10](I)=[C:9]([O:14][CH3:15])[C:8](=[O:16])[NH:7][C:6]=2[CH:17]=1.C([Sn](CCCC)(CCCC)[C:23]1[CH:28]=[CH:27][C:26]([N+:29]([O-:31])=[O:30])=[CH:25][CH:24]=1)CCC>C1(C)C=CC=CC=1.[CH2-]C1C=CC=CC=1.C1C=CC(P(C2C=CC=CC=2)C2C=CC=CC=2)=CC=1.C1C=CC(P(C2C=CC=CC=2)C2C=CC=CC=2)=CC=1.Cl[Pd+]>[Cl:1][C:2]1[CH:3]=[CH:4][C:5]2[C:11](=[O:12])[C:10]([C:23]3[CH:28]=[CH:27][C:26]([N+:29]([O-:31])=[O:30])=[CH:25][CH:24]=3)=[C:9]([O:14][CH3:15])[C:8](=[O:16])[NH:7][C:6]=2[CH:17]=1

Participants

5

Reactant 2

HCID 10993313Stannane, tributyl(4-nitrophenyl)-HCID 18980002HCID 18980002, compound

Product 1

HCID 189800568-Chloro-3-methoxy-4-(4-nitrophenyl)-2,5-dioxo-2,5-dihydro-1H-benz[b]azepineYield 61%

Reagents, catalysts & solvents 2

HCID 11007180Palladium(2+) chloride phenylmethanide--triphenylphosphane (1/1/1/2)CatalystHCID 1140TolueneSolvent

Procedure

8-Chloro-4-iodo-3-methoxy-2,5-dioxo-2,5-dihydro-1H-benz[b]azepine (0.50 g) was dissolved in toluene (12 mL). To this stirred suspension was added trans-benzyl(chloro)bis(triphenylphosphine)palladium(II) (0.050 g) and tributyl(4-nitrophenyl)tin (0.70 g). The resulting suspension was stirred at reflux for 48 hours, then cooled to room temperature, applied directly to a silica column (1.5 cm by 15 cm), and eluted with dichloromethane (250 mL), (ether:dichloromethane (20:80)(250 mL), and methanol:dichloromethane (5:95)(250 mL) to afford the title product (0.30 g, 61%) as a light green solid; mp 250°-251° C. (dec); NMR: 8.24 (d,2, J=9.0), 7.68 (d,1, J=8.6), 7.54 (d,2, J=8.9), 7.42 (d,1, J=2.0), 7.32 (dd,1, J=9.0, 2.1), 3.72 (s,3); MS: m/z=359(M+1).

Workup

  1. temperatureat reflux for 48 hours
  2. washeluted with dichloromethane (250 mL)

Sources & evidence

ORD record
ord-a26f7d94606a47f18972d9488e4e84cc
Source dataset
uspto-grants-1997_08
Patent number
US05656626

Reaction notes

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