Diethyl Ether → HCID 11013069, compound

HRID 260401Notes

Reaction equation

HRID 260401 reaction equation
[OH:1][C:2]1[CH:15]=[CH:14][C:13]2[C:4](=[C:5]3[C:10](=[CH:11][N:12]=2)[CH2:9][CH2:8][CH2:7][CH2:6]3)[CH:3]=1.[N+:16]([C:19]1[CH:26]=[CH:25][CH:24]=[CH:23][C:20]=1[CH2:21]Br)([O-:18])=[O:17].C(=O)([O-])[O-].[K+].[K+].C(OCC)C>[I-].C([N+](CCCC)(CCCC)CCCC)CCC.CN(C=O)C.O.ClCCl>[N+:16]([C:19]1[CH:26]=[CH:25][CH:24]=[CH:23][C:20]=1[CH2:21][O:1][C:2]1[CH:15]=[CH:14][C:13]2[C:4](=[C:5]3[C:10](=[CH:11][N:12]=2)[CH2:9][CH2:8][CH2:7][CH2:6]3)[CH:3]=1)([O-:18])=[O:17]

Participants

9

Reactant 4

HCID 3283Diethyl EtherHCID 11430Potassium CarbonateHCID 77569alpha-Bromo-2-nitrotolueneHCID 110743862-Phenanthridinol, 7,8,9,10-tetrahydro-

Product 1

HCID 11013069HCID 11013069, compoundYield 94.2%

Reagents, catalysts & solvents 4

HCID 67553Tetrabutylammonium IodideCatalystHCID 962WaterSolventHCID 6228DimethylformamideSolventHCID 6344DichloromethaneSolvent

Conditions

Temperature
25 °C

Procedure

A mixture of Compound 275 (57.17 g, 287 mmol) , 2-nitrobenzyl bromide (68.19 g, 316 mmol), powdered potassium carbonate (142.0 g, 1.03 mol) and tetra-n-butylammonium iodide (3.18 g, 8.61 mmol) in dry DMF (400 mL) was stirred at 25° C. for 3 hours and then poured into a mixture of ethyl ether (200 mL), dichloromethane (1500 mL), and water (200 mL) with stirring. After allowing this mixture to settle, the aqueous layer was discarded. The organic layer was washed with water (3×1500 mL), dried (MgSO4), and filtered through a 8 cm×8 cm plug of silica with rinsing with ethyl ether (300 mL). The combined filtrates were evaportated in vacuo, and the residue was purified by recrystallization from chloroform-ethyl ether to give 90.41 g (94 percent) of Compound 276: off-white crystalline solid; mp 153°-154° C. Rf=0.48 (silica, 40 percent ethyl acetate in dichloromethane); IR (CHCl3) νmax 2939, 1619, 1526, 1508, 1433, 1342 cm-1 ; 1H NMR (300 MHz, CDCl3) δ 8.50 (s, 1 H, H6), 8.19 (dd, J=7.4, 1.0 Hz, 1 H, aromatic), 7.99 (d, J=9.1 Hz, 1 H, H4), 7.97 (dd, J=7.4, 1.0 Hz, 1 H, aromatic), 7.71 (td, J=7.4, 1.0 Hz, 1 H, aromatic), 7.52 (td, J=7.4, 1.0 Hz, 1 H, aromatic), 7.39 (dd, J=9.1, 2.8 Hz, 1 H, H3), 7.24 (d, J=2.8 Hz, 1 H, H1), 5.61 (s, 2 H, benzylic), 2.99 (t, J= 6.1 Hz, 2 H, H7 or H10), 2.88 (t, J=6.1 Hz, 2 H, H7 or H10), 2.01-1.84 (m, 4 H, H8 and H9); --C NMR (125 MHz, CDCl3) δ 156.0, 150.3, 146.9, 142.4, 140.0, 134.0, 133.9, 133.4, 131.5, 130.1, 128.5, 128.4, 124.9, 119.8, 102.7, 66.7, 27.1, 24.9, 22.3, 22.2; MS (FAB+) m/e (rel intensity) 335 (M+H, 100), 200 (13); HRMS for C20H19N2O3 (M+H), calcd 335.1396, found 335.1394.

Workup

  1. stirringwith stirring
  2. washThe organic layer was washed with water (3×1500 mL)
  3. dry with materialdried (MgSO4)
  4. filtrationfiltered through a 8 cm×8 cm plug of silica
  5. washwith rinsing with ethyl ether (300 mL)
  6. customthe residue was purified by recrystallization from chloroform-ethyl ether

Sources & evidence

ORD record
ord-71de948bd5604b8aa25948ad0f0c1ff6
Source dataset
uspto-grants-1996_06
Patent number
US05527805

Reaction notes

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