Dichlorodimethylsilane → HCID 21709887, compound

HRID 650887Notes

Reaction equation

HRID 650887 reaction equation
[O:1]([C:9]1[CH2:10][C:11]2[C:16]([CH:17]=1)=[CH:15][CH:14]=[CH:13][CH:12]=2)[Si:2]([C:5]([CH3:8])([CH3:7])[CH3:6])([CH3:4])[CH3:3].[Li][CH2:19][CH2:20][CH2:21][CH3:22].[CH3:23][Si:24]([CH3:27])(Cl)Cl>CCOCC.CCCCCC>[CH3:23][Si:24]([CH3:27])([CH:19]1[C:16]2[C:22](=[CH:11][CH:10]=[CH:9][CH:17]=2)[CH:21]=[C:20]1[O:1][Si:2]([C:5]([CH3:8])([CH3:7])[CH3:6])([CH3:4])[CH3:3])[CH:17]1[C:16]2[C:11](=[CH:12][CH:13]=[CH:14][CH:15]=2)[CH:10]=[C:9]1[O:1][Si:2]([C:5]([CH3:8])([CH3:7])[CH3:6])([CH3:4])[CH3:3]

Participants

6

Reactant 3

HCID 6398DichlorodimethylsilaneHCID 21709896HCID 21709896, compoundHCID 178418339Butyllithium

Product 1

HCID 21709887HCID 21709887, compoundYield 42.1%

Reagents, catalysts & solvents 2

HCID 3283Diethyl EtherSolvent2×HCID 8058HexaneSolvent

Procedure

To a solution of 2-(tert-butyldimethylsiloxy)indene (12.32 g, 50.0 mmol) in Et2O (50 mL) at 0° C. was added dropwise n-BuLi (20.0 mL of a 2.5 M solution in hexane, 50.0 mmol) and the reaction mixture was stirred overnight at room temperature. The resulting solution was then added dropwise to a solution of dimethyldichlorosilane (3.03 mL, 25.0 mmol) in Et2O (25 mL) at 0° C. The reaction mixture was stirred overnight at room temperature and washed with saturated ammonium chloride solution (150 mL), water (3×100 mL) and dried over sodium sulfate. Evaporation of the solvents left a red oil that was dissolved in a 1:1 mixture of MeOH and acetone. Concentration and cooling to −30° C. gave 5.78 g (42.1%) of the title compound as slightly yellow crystals. The first crop consisted exclusively of the racemic diastereomer. EIMS (calcd/found): m/e 548.2962/548.2958. Mp: 92-94° C. 1H NMR (CDCl3, δ): 7.22-7.14 (m, 6H); 6.98 (td, 3J=7.3 Hz, 4J=1.4 Hz, 2H); 5.85 (s, 2H); 3.99 (s, 2H); 0.97 (s, 18H); 0.34 (s, 6H); 0.28 (s, 6H); −0.23 (s, 6H). 13C NMR (CDCl3, δ): 164.96; 144.44; 137.55; 125.13; 122.75; 121.41; 118.83; 104.00; 43.06; 25.77; 18.20; 4.34; −4.88; −6.99. The oily residue was washed with copiously with cold MeOH (3×50 mL), cold pentane (50 mL) and dried in vacuo to yield 3.47 g (24.8%) of the fairly pure meso diastereomer as a red oil (total yield 66.9%).

Workup

  1. stirringThe reaction mixture was stirred overnight at room temperature
  2. washwashed with saturated ammonium chloride solution (150 mL), water (3×100 mL)
  3. dry with materialdried over sodium sulfate
  4. customEvaporation of the solvents
  5. waitleft a red oil that
  6. dissolutionwas dissolved in a 1:1 mixture of MeOH and acetone
  7. concentrationConcentration
  8. temperaturecooling to −30° C.

Sources & evidence

ORD record
ord-44b49f2f86504f8f8c730a48b46a0f33
Source dataset
uspto-grants-2001_08
Patent number
US06277778B1

Reaction notes

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