2-Methyl-7-(4'-tert-butylphenyl)indene → [4-(4-tert-Butylphenyl)-2-methyl-1H-inden-1-yl][6-isopropyl-2-methyl-5-(pentafluoro phenoxy)-4-phenyl-1H-inden-1-yl]dimethylsilane

HRID 716451Notes

Reaction equation

HRID 716451 reaction equation
[C:1]([C:5]1[CH:10]=[CH:9][C:8]([C:11]2[CH:12]=[CH:13][CH:14]=[C:15]3[C:19]=2[CH2:18][C:17]([CH3:20])=[CH:16]3)=[CH:7][CH:6]=1)([CH3:4])([CH3:3])[CH3:2].[Li]CCCC.C([Cu])#N.Cl[Si:30]([CH:33]1[C:41]2[C:36](=[C:37]([C:57]3[CH:62]=[CH:61][CH:60]=[CH:59][CH:58]=3)[C:38]([O:45][C:46]3[C:51]([F:52])=[C:50]([F:53])[C:49]([F:54])=[C:48]([F:55])[C:47]=3[F:56])=[C:39]([CH:42]([CH3:44])[CH3:43])[CH:40]=2)[CH:35]=[C:34]1[CH3:63])([CH3:32])[CH3:31]>CCOCC.O>[C:1]([C:5]1[CH:10]=[CH:9][C:8]([C:11]2[CH:12]=[CH:13][CH:14]=[C:15]3[C:19]=2[CH:18]=[C:17]([CH3:20])[CH:16]3[Si:30]([CH:33]2[C:41]3[C:36](=[C:37]([C:57]4[CH:62]=[CH:61][CH:60]=[CH:59][CH:58]=4)[C:38]([O:45][C:46]4[C:51]([F:52])=[C:50]([F:53])[C:49]([F:54])=[C:48]([F:55])[C:47]=4[F:56])=[C:39]([CH:42]([CH3:44])[CH3:43])[CH:40]=3)[CH:35]=[C:34]2[CH3:63])([CH3:31])[CH3:32])=[CH:7][CH:6]=1)([CH3:4])([CH3:2])[CH3:3]

Participants

7

Reactant 4

HCID 103553602-Methyl-7-(4'-tert-butylphenyl)indeneHCID 89392521Chloro[6-isopropyl-2-methyl-5-(pentafluorophenoxy)-4-phenyl-1H-inden-1-yl]dimethylsilaneHCID 178418339ButyllithiumHCID 178418546HCID 178418546, compound

Product 1

HCID 89392493[4-(4-tert-Butylphenyl)-2-methyl-1H-inden-1-yl][6-isopropyl-2-methyl-5-(pentafluoro phenoxy)-4-phenyl-1H-inden-1-yl]dimethylsilaneYield 53%

Reagents, catalysts & solvents 2

HCID 962WaterSolventHCID 3283Diethyl EtherSolvent2×

Procedure

To a solution of 6.39 g (24.4 mmol) of 7-(4-tert-butylphenyl)-2-methyl-1H-indene in 200 ml of ether 9.80 ml (24.5 mmol) of 2.5 M nBuLi in hexanes was added in one portion at −40° C. This mixture was stirred overnight at room temperature, then cooled to −40° C., and 150 mg of CuCN was added. The resulting mixture was stirred for 1 h at −20° C., then cooled to −40° C., and a solution of 10.5 g (20.0 mmol) of chloro[6-isopropyl-2-methyl-5-(pentafluorophenoxy)-4-phenyl-1H-inden-1-yl]dimethylsilane in 200 ml of ether was added in one portion. Further on, this mixture was stirred overnight at ambient temperature, then 0.5 ml of water was added. This solution was filtered through a pad of silica gel 60 (40-63 um) which was then additionally washed by 2×75 ml of dichloromethane. The combined organic elute was evaporated to dryness, and the residue was dried in vacuum. The product was isolated by flash-chromatography on silica gel 60 (40-63 um; eluent: hexanes-dichloromethane=10:1, vol., then 5:1, vol.). This procedure gave 7.86 g (53%) of the title product (of ca. 90% purity as a ca. 1:1 mixture of the stereoisomers on the evidence of NMR spectroscopy) as a yellowish glass.

Workup

  1. temperaturecooled to −40° C.
  2. stirringThe resulting mixture was stirred for 1 h at −20° C.
  3. temperaturecooled to −40° C.
  4. stirringFurther on, this mixture was stirred overnight at ambient temperature
  5. filtrationThis solution was filtered through a pad of silica gel 60 (40-63 um) which
  6. washwas then additionally washed by 2×75 ml of dichloromethane
  7. washThe combined organic elute
  8. customwas evaporated to dryness
  9. customthe residue was dried in vacuum
  10. customThe product was isolated by flash-chromatography on silica gel 60 (40-63 um

Sources & evidence

ORD record
ord-f4f695c297b64090878aab48a0c3354c
Source dataset
uspto-grants-2015_11
Patent number
US09187583B2

Reaction notes

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