HCID 86614874, compound → HCID 86614875, compound

HRID 2117991Notes

Reaction equation

HRID 2117991 reaction equation
[CH3:1][Li].[Cl:3][C:4]1[CH:5]=[C:6]2[C:36](=[CH:37][CH:38]=1)[C:14]1[N:15]([CH2:28][O:29][CH2:30][CH2:31][Si:32]([CH3:35])([CH3:34])[CH3:33])[C:16]([C:18]3[C:25]([C:26]#[N:27])=[CH:24][CH:23]=[CH:22][C:19]=3[C:20]#[N:21])=[N:17][C:13]=1[C:12]1[CH:11]=[CH:10][C:9]([CH2:39][C:40](=[O:42])[CH3:41])=[CH:8][C:7]2=1>C(OCC)C.Cl[Ti](Cl)(Cl)Cl>[Cl:3][C:4]1[CH:5]=[C:6]2[C:36](=[CH:37][CH:38]=1)[C:14]1[N:15]([CH2:28][O:29][CH2:30][CH2:31][Si:32]([CH3:34])([CH3:33])[CH3:35])[C:16]([C:18]3[C:25]([C:26]#[N:27])=[CH:24][CH:23]=[CH:22][C:19]=3[C:20]#[N:21])=[N:17][C:13]=1[C:12]1[CH:11]=[CH:10][C:9]([CH2:39][C:40]([OH:42])([CH3:1])[CH3:41])=[CH:8][C:7]2=1

Participants

5

Reactant 2

HCID 86614874HCID 86614874, compoundHCID 178418348HCID 178418348, compound

Product 1

HCID 86614875HCID 86614875, compound

Reagents, catalysts & solvents 2

HCID 24193Titanium TetrachlorideCatalystHCID 3283Diethyl EtherSolvent

Conditions

Temperature
-78 °C

Procedure

To a round bottomed flask at −78° C. charged with TiCl4 (1 M in CH2Cl2, 20 mL), was added methyllithium (1.6 M in diethyl ether, 12.5 mL). The resulting deep red solution was stirred at −78° C. for 15 minutes and then added via cannula to a 0° C. solution of 2-(9-chloro-6-(2-oxopropyl)-1-{[2-(trimethylsilyl)ethoxy]methyl)-1H-phenanthro[9,10-d]imidazol-2-yl)isophthalonitrile (2.8 g, 5.0 mmol) from Step 2 above, in diethyl ether (10 mL). The resulting mixture was stirred at 0° C. for 3 h, then quenched with saturated ammonium chloride. The aqueous layer was extracted with ethyl acetate. The organic layer washed with brine, dried over MgSO4, filtered and concentrated. The crude material was purified by flash chromatography on silica (50% ethyl acetate in hexanes) to provide 2-(9-chloro-6-(2 -hydroxy-2-methylpropyl)-1-{[2-(trimethylsilyl)ethoxy]methyl}-1H-phenanthro[9,10-d]imidazol-2-yl)isophthalonitrile (1.94 g),

Workup

  1. stirringThe resulting mixture was stirred at 0° C. for 3 h
  2. customquenched with saturated ammonium chloride
  3. extractionThe aqueous layer was extracted with ethyl acetate
  4. washThe organic layer washed with brine
  5. dry with materialdried over MgSO4
  6. filtrationfiltered
  7. concentrationconcentrated
  8. customThe crude material was purified by flash chromatography on silica (50% ethyl acetate in hexanes)

Sources & evidence

ORD record
ord-4acda22021b04d85b1b38d88aca4123d
Source dataset
uspto-grants-2008_10
Patent number
US07442716B2

Reaction notes

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