Chlorotrimethylsilane → HCID 13955049, compound

HRID 232439Notes

Reaction equation

HRID 232439 reaction equation
Cl[Si](C)(C)C.[H-].[Al+3].[Li+].[H-].[H-].[H-].[CH2:12]([P:19]([CH2:27][C:28]12O[C:29]1([C:35]1[CH:40]=[CH:39][CH:38]=[CH:37][C:36]=1[CH2:41][P:42]([CH2:50][C:51]1[CH:56]=[CH:55][CH:54]=[CH:53][CH:52]=1)[CH2:43][C:44]1[CH:49]=[CH:48][CH:47]=[CH:46][CH:45]=1)[CH:30]=[CH:31][CH:32]1O[CH:33]12)[CH2:20][C:21]1[CH:26]=[CH:25][CH:24]=[CH:23][CH:22]=1)[C:13]1[CH:18]=[CH:17][CH:16]=[CH:15][CH:14]=1>C1COCC1>[CH2:50]([P:42]([CH2:41][C:36]1[CH:37]=[CH:38][CH:39]=[CH:40][C:35]=1[C:29]1[CH:30]=[CH:31][CH:32]=[CH:33][C:28]=1[CH2:27][P:19]([CH2:12][C:13]1[CH:14]=[CH:15][CH:16]=[CH:17][CH:18]=1)[CH2:20][C:21]1[CH:22]=[CH:23][CH:24]=[CH:25][CH:26]=1)[CH2:43][C:44]1[CH:49]=[CH:48][CH:47]=[CH:46][CH:45]=1)[C:51]1[CH:56]=[CH:55][CH:54]=[CH:53][CH:52]=1

Participants

5

Reactant 3

HCID 6397ChlorotrimethylsilaneHCID 21226445Aluminium lithium hydrideHCID 86741800HCID 86741800, compound

Product 1

HCID 13955049HCID 13955049, compoundYield 62%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent2×

Conditions

Temperature
-35 °C

Procedure

Chlorotrimethylsilane (4.1 ml, 32.2 mmol) was added to lithium aluminum hydride (1.22 grams, 32.2 mmol) in THF (20 ml) at -72° C. The mixture was removed from the cold bath, stirred 2 hours, and then cooled again at -35° C. A suspension of the above 2,2'-bis(dibenzylphosphinomethyl)-1,1'-biphenyl dioxide (3.40 grams, 5.32 mmol) in THF (45 ml) was added by cannula. The mixture was stirred 0.5 hour at -30° C., then overnight at room temperature. The reaction mixture was cooled in an ice bath and quenched by the successive, dropwise addition of water (1.2 ml), 15% aqueous NaOH (1.2 ml) and water (3.6 ml). The resulting mixture was filtered, and the solid was washed with diethyl ether. The filtrate was evaporated on the steam bath under a stream of nitrogen. The residual solid was heated in ethanol, then cooled and filtered to give 2.00 grams (62% yield) of white solid, melting point 163° to 167° C. 1H NMR (CDCl3): δ 2.43 (s, 12H, benzylic); 6.50-7.17 (complex, 28H, aromatic). 31P NMR (CDCl3): δ+9.5.

Workup

  1. customThe mixture was removed from the cold bath
  2. additionwas added by cannula
  3. stirringThe mixture was stirred 0.5 hour at -30° C.
  4. customovernight
  5. customat room temperature
  6. temperatureThe reaction mixture was cooled in an ice bath
  7. customquenched by the successive,
  8. additiondropwise addition of water (1.2 ml), 15% aqueous NaOH (1.2 ml) and water (3.6 ml)
  9. filtrationThe resulting mixture was filtered
  10. washthe solid was washed with diethyl ether
  11. customThe filtrate was evaporated on the steam bath under a stream of nitrogen
  12. temperatureThe residual solid was heated in ethanol
  13. temperaturecooled
  14. filtrationfiltered

Sources & evidence

ORD record
ord-4b5fc1bbad3a4a85a800f6067f474433
Source dataset
uspto-grants-1989_07
Patent number
US04851581

Reaction notes

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