Water → 10-[(tert-Butyldimethylsilyl)oxy]-3-[(2-nitrobenzyl)oxy]-7,8,9,10-tetrahydrophenanthridine

HRID 260393Notes

Reaction equation

HRID 260393 reaction equation
[Si:1]([O:8][CH:9]1[C:22]2[C:13](=[CH:14][N:15]=[C:16]3[C:21]=2[CH:20]=[CH:19][C:18]([OH:23])=[CH:17]3)[CH2:12][CH2:11][CH2:10]1)([C:4]([CH3:7])([CH3:6])[CH3:5])([CH3:3])[CH3:2].[H-].[Na+].[N+:26]([C:29]1[CH:36]=[CH:35][CH:34]=[CH:33][C:30]=1[CH2:31]Br)([O-:28])=[O:27].O>C1COCC1.[I-].C([N+](CCCC)(CCCC)CCCC)CCC>[Si:1]([O:8][CH:9]1[C:22]2[C:13](=[CH:14][N:15]=[C:16]3[C:21]=2[CH:20]=[CH:19][C:18]([O:23][CH2:31][C:30]2[CH:33]=[CH:34][CH:35]=[CH:36][C:29]=2[N+:26]([O-:28])=[O:27])=[CH:17]3)[CH2:12][CH2:11][CH2:10]1)([C:4]([CH3:7])([CH3:6])[CH3:5])([CH3:3])[CH3:2]

Participants

7

Reactant 4

HCID 962WaterHCID 24758Sodium hydrideHCID 77569alpha-Bromo-2-nitrotolueneHCID 13576196710-[(tert-Butyldimethylsilyl)oxy]-3-hydroxy-7,8,9,10-tetrahydrophenanthridine

Product 1

HCID 1503834510-[(tert-Butyldimethylsilyl)oxy]-3-[(2-nitrobenzyl)oxy]-7,8,9,10-tetrahydrophenanthridineYield 90.2%

Reagents, catalysts & solvents 2

HCID 67553Tetrabutylammonium IodideCatalystHCID 8028TetrahydrofuranSolvent

Procedure

To a suspension of Compound 141a (1.00 g, 3.03 mmol) in dry THF (20 mL) cooled in an ice-water bath was added NaH (60 percent, 128 mg, 3.19 mmol) followed by stirring for 10 minutes. To the resultant solution was added 2-nitrobenzyl bromide (0.689 g, 3.19 mmol) and tetra-n-butylammonium iodide (0.11 g, 0.3 mmol), and the mixture was then stirred at 25° C. for one hour. Water was added to the reaction mixture followed by extraction with ethyl acetate (50 mL), washing with brine, dry over anhydrous Na2SO4, and concentration in vacuo to give a crude product. Flash column chromatography of the crude product (silica gel, 20 percent ethyl ether in benzene) afforded Compound 143a (1.27 g, 90 percent): pale-yellow solid; mp 150°-152° C.; Rf =0.33 (silica, 20 percent ethyl ether in benzene); IR (CHCl3) νmax 2953, 2933, 1623, 1528, 1343, 1090, 1027, 838 cm-1 ; 1H NMR (300 MHz, CDCl3) δ 8.60 (s, 1 H, H6), 8.21 (dd, J=8.0, 0.9 Hz, 1 H, aromatic), 8.01 (d, J=9.2 Hz, 1 H, H1), 7.92 (d, J=7.8 Hz, 1 H, aromatic), 7.68 (dt, J=7.8, 0.9 Hz, 1 H, aromatic), 7.50 (t, J=8.0 Hz, 1 H, aromatic), 7.44 (d, J=2.6 Hz, 1 H, H4), 7.32 (dd, J=9.2, 2.6 Hz, 1 H, H2), 5.66 (s, 2 H, benzylic), 5.42 (t, J=3.1 Hz, 1 H, H10), 2.97 (br dd, J=14.0, 4.0 Hz, 1 H, H7), 2.86-2.72 (m, 1 H, H7), 2.25-2.15 (m, 2 H, H8 or H9), 1.90-1.80 (m, 2 H, H8 or H9), 0.85 (s, 9 H, SiC(CH3)3), 0.22 (s, 6 H, Si(CH3)2); MS (FAB+) m/e (rel intensity) 465 (M+Cs, 100), 407 (19), 330 (26), 198 (17), 136 (18); HRMS for C26H32N2O4SiCs (M+Cs), calcd 465.2210, found 465.2210. Anal. Calcd for C26H32N2O4Si: C, 67.21; H, 6.94; N, 6.03. Found: C, 67.31; H, 6.91; N, 5.96.

Workup

  1. temperaturecooled in an ice-water bath
  2. stirringthe mixture was then stirred at 25° C. for one hour
  3. extractionfollowed by extraction with ethyl acetate (50 mL)
  4. washwashing with brine
  5. dry with materialdry over anhydrous Na2SO4, and concentration in vacuo
  6. customto give a crude product

Sources & evidence

ORD record
ord-2f393e4b3d4840a694180cd0fa7d0dd5
Source dataset
uspto-grants-1996_06
Patent number
US05527805

Reaction notes

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