Reaction equation
[Br:1][C:2]1[CH2:3][CH:4]2[C:9](=[C:10]([N+:12]([O-])=O)[CH:11]=1)[N:8]([C:15]([C:17](OCC)=[O:18])=[O:16])[CH:7]([CH2:22][C:23]([O:25][CH3:26])=[O:24])[CH2:6][CH2:5]2>CC(C)=O.O.[Cl-].[Cl-].[Cl-].[Ti+3]>[Br:1][C:2]1[CH:3]=[C:4]2[CH2:5][CH2:6][CH:7]([CH2:22][C:23]([O:25][CH3:26])=[O:24])[N:8]3[C:15](=[O:16])[C:17](=[O:18])[NH:12][C:10]([CH:11]=1)=[C:9]23Participants
Reactant 1
Product 1
Reagents, catalysts & solvents 3
Conditions
- Temperature
- 0 °C
Procedure
To a mixture of 20% aqueous titanium trichloride (540 g, 0.7 mol), water (500 mL), and acetone (500 mL) was added dropwise 6-bromo-2-methoxycarbonylmethyl-8-nitro-N-ethoxalyltetrahydroquinoline (46 g, obtained above) in acetone (500 mL) over 1 h at 0° C. The mixture was stirred for 3 h at 0° C., diluted with water (1 L) and extracted with dichloromethane (1 L and 500 mL). The organic layers were washed successively with 1N hydrochloric acid, water, and brine, dried over magnesium sulfate, and concentrated. The residual solid was rinsed with a 1:1 mixture of hexane and toluene (400 mL) to give 17.4 g of the title compound (49% from 2-methoxycarbonylmethyltetrahydroquinoline hydrochloride): mp 185°~187° C.; 1H NMR (270 MHz, DMSO-d6) δ12.04 (bs, 1H), 7.20 (d, 1H, J=2 Hz), 7.15 (d, 1H, J=2 Hz), 5.04~5.13 (m, 1H), 3.62 (s, 3H), 2.94 (ddd, 1H, J=17.1, 13.5, 4.5 Hz), 2.78 (dm, 1H, J=17.1 Hz), 2.63 (dd, 1H, J =18, 7.2 Hz), 2.57 (dd, 1H, J=18, 3.6 Hz), 2.09 (dm, 1H, J=13.5 Hz), 1.80~1.95 (m, 1H).
Workup
- extractionextracted with dichloromethane (1 L and 500 mL)
- washThe organic layers were washed successively with 1N hydrochloric acid, water, and brine
- dry with materialdried over magnesium sulfate
- concentrationconcentrated
- washThe residual solid was rinsed with a 1:1 mixture of hexane and toluene (400 mL)
Sources & evidence
- ORD record
- ord-6245e9d57e5e409694559f1a533cdef4
- Source dataset
- uspto-grants-1997_04
- Patent number
- US05616586
Linked notes
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