Réaction #809152

Équation de réaction

Chlorotrimethylsilane

thianthrene-5-oxide

n-butyl lithium

diisopropylamine

→

crystals

Rendement 36.1%

4,6-Bis(trimethylsilyl)thianthrene-5-oxide

Rendement 36.1%

Solvants

Water

THF

lithium diisopropylamide

THF

Conditions de réaction

Traitement

1. 1
   workup.ADDITIONwas added in portion at −78° C. under inert atmosphere
2. 2
   workup.STIRRINGstirred overnight
3. 3
   Autreto quench the excess base
4. 4
   AutreThe solvent was removed
5. 5
   workup.DISSOLUTIONthe crude mixture was redissolved in ether
6. 6
   ExtractionThe aqueous layer was extracted by ether
7. 7
   LavageIt was further washed by water, brine
8. 8
   Séchagedried with MgSO4
9. 9
   AutreThe solvent was then removed in vacuo
10. 10
    AutreThe crude product was further purified by column chromatography (hexane/CH2Cl2 4/1

Mode opératoire

To a stirred solution of thianthrene-5-oxide (9.40 g, 40.5 mmole) in THF (200 mL), lithium diisopropylamide (prepared by the addition of n-butyl lithium (1.6 M, 64.0 mL, 101 mmole) to a solution of diisopropylamine (14.2 mL, 101 mmole) at −78° C.) in THF (100 mL) was added in portion at −78° C. under inert atmosphere. The reaction mixture was stirred at this temperature for 4 hrs and became dark green. Chlorotrimethylsilane (12.8 mL, 101 mmole) was then added to the cold solution. The solution was then turned into yellowish brown, warmed back to room temperature, and stirred overnight. Water (100 mL) was then added to the reaction mixture to quench the excess base. The solvent was removed and the crude mixture was redissolved in ether. The aqueous layer was extracted by ether and the organic layers were combined. It was further washed by water, brine, and dried with MgSO4. The solvent was then removed in vacuo. The crude product was further purified by column chromatography (hexane/CH2Cl2 4/1, and then 2/1) to afford light yellow crystals (5.50 g, 36%). mp 210˜211° C. (lit. 213˜214° C.). 1H NMR (300 MHz, CDCl3) δ: 7.69 (dd, 2H, J=7.8, 1.5 Hz), 7.60 (dd, 2H, J=7.8, 1.5 Hz), 7.41 (dd, 2H, J=7.8, 7.8 Hz), 0.57 (s, 18H). 13C NMR (125 MHz, CDCl3) δ: 144.1, 140.9, 134.0, 133.8, 129.9, 129.3, 1.55. HR-MS (ESI): calcd. for C18H24OS2Si2+Na 399.0699 [(M+Na)+]. found 399.0690.

Source