Reaktion #2480153

Reaktionsgleichung

Lithium aluminum hydride

triethylamine

3-chloropropyl 3-(tert-butyldimethylsilyloxy)benzoate

adamantanone

→

product

[(3-tert-butyldimethylsilyloxylphenyl)-(3-chloropropoxy)methylene]tricyclo[3.3.1.13,7 ]decane

Lösungsmittel

water

THF

THF

Reaktionsbedingungen

Aufarbeitung

1. 1
   workup.ADDITIONAfter the addition
2. 2
   Temperaturthe reaction mixture was refluxed for 2 h
3. 3
   TemperaturHeating
4. 4
   Extraktionextracted with 3×300 mL of hexane
5. 5
   FiltrationThe combined organic solutions were filtered
6. 6
   Trocknendried over sodium sulfate
7. 7
   Einengenconcentrated under reduced pressure
8. 8
   SonstigeThe residue was partially purified by flash chromatography (2% ethyl acetate/hexane)

Vorschrift

Titanium trichloride (25.8 g, 0.167 mol) was added to dry THF (500 mL) in a dried 3 L three-necked flask under a head of Ar at 0° C. Lithium aluminum hydride (3.01 g, 0.084 mol) was added in small portions with vigorous stirring. The reaction mixture was warmed to room temperature and 23.3 mL of triethylamine was added dropwise. After the addition was completed, the reaction mixture was refluxed for 2 h. Heating was stopped and a solution of 3-chloropropyl 3-(tert-butyldimethylsilyloxy)benzoate (5.28 g, 0.016 mol) and adamantanone (7.23 g, 0.048 mol) in 100 mL of dry THF was added dropwise to the refluxing mixture over a 45 min period. The reaction mixture was stirred over night at room temperature. The black mixture was diluted with water and extracted with 3×300 mL of hexane. The combined organic solutions were filtered, dried over sodium sulfate and concentrated under reduced pressure. The residue was partially purified by flash chromatography (2% ethyl acetate/hexane) to give the product as a viscous oil which was taken on to the next step. 1H NMR (CDCl3) δ0.200 (S, 6H), 0.988 (S, 9H), 1.66-2.01 (m, 14H), 2.63 (br s, 1H), 3.23 (br s, 1H), 3.538 (t, 2H, J=5.7 Hz), 3.640 (t, 2H, J=6.6 Hz), 6.75-7.22 (m, 4H). ##STR23##

Quelle