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

HRID 721970

Reaktionsgleichung

Reaktionsgleichung von HRID 721970
[CH:1]1[C:14]2[S:13][C:12]3[C:7](=[CH:8][CH:9]=[CH:10][CH:11]=3)[S:6](=[O:15])[C:5]=2[CH:4]=[CH:3][CH:2]=1.C([Li])CCC.C(NC(C)C)(C)C.Cl[Si:29]([CH3:32])([CH3:31])[CH3:30]>C1COCC1.C([N-]C(C)C)(C)C.[Li+].O>[CH3:30][Si:29]([CH3:32])([CH3:31])[C:4]1[C:5]2[S:6](=[O:15])[C:7]3[C:12](=[CH:11][CH:10]=[CH:9][C:8]=3[Si:29]([CH3:32])([CH3:31])[CH3:30])[S:13][C:14]=2[CH:1]=[CH:2][CH:3]=1

Komponenten

8

Edukt 4

HCID 6397ChlorotrimethylsilaneHCID 7912DiisopropylamineHCID 73220Thianthrene, 5-oxideHCID 178418339Butyllithium

Produkt 1

HCID 150826654,6-Bis(trimethylsilyl)thianthrene-5-oxideAusbeute 36,1 %

Reagenzien, Katalysatoren, Lösungsmittel 3

HCID 962WaterLösungsmittelHCID 8028TetrahydrofuranLösungsmittel2×HCID 2724682Lithium diisopropylamideLösungsmittel

Versuchsvorschrift

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.

Aufarbeitung

  1. additionwas added in portion at −78° C. under inert atmosphere
  2. stirringstirred overnight
  3. customto quench the excess base
  4. customThe solvent was removed
  5. dissolutionthe crude mixture was redissolved in ether
  6. extractionThe aqueous layer was extracted by ether
  7. washIt was further washed by water, brine
  8. dry with materialdried with MgSO4
  9. customThe solvent was then removed in vacuo
  10. customThe crude product was further purified by column chromatography (hexane/CH2Cl2 4/1

Quellen und Nachweise

ORD-Eintrag
ord-33e1ded494eb41b0880aec5100c9edf0
Quelldatensatz
uspto-grants-2006_11
Patentnummer
US07138075B2

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