Triphenylphosphine → HCID 14154745, Verbindung

To a THF (300 mL) solution of triphenyl-phosphine (42 g, 160 mmol, 2 equiv) at 0° C. was added diisopropyl azodicarboxylate (32 mL, 162 mmol) to produce a pale yellow solid. A THF (300 mL) solution of 3-quinuclidinol (10.2 g, 80.2 mmol) and thiolacetic acid was added dropwise to the yellow reaction mixture and stirred overnight. THF was removed in vacuo and the residue was dissolved in ether (500 mL) and extracted with 10% HCl (4×150 mL). The aqueous acidic phase was back extracted with ether/ethyl acetate (75 mL/25 mL) and then neutralized to pH 7 by the addition of sodium bicarbonate cautiously in small portions. The aqueous layer was then basified to pH 9-10 by adding a few drops of 10N NaOH, then extracted with dichlormethane (5×200 mL), dried over anhydrous sodium sulfate and concentrated. Purification by flash column chromatrography using 5% MeOH in chloroform as eluent gave 3-acetylthioquinuclidine (10.5 g, 71%). 1H (300 MHz, CDCl3): δ 3.725-3.63 (m, 1H), 3.427 (dd, 10.23 Hz, 13.7 Hz), 2.9-2.75 (dd, 4H), 2.678 (dd, 5.7 Hz, 14.2 Hz, 1H), 2.326 (S, 3H), 1.9-1.82 (m, 1H), 1.81-1.675 (m, 3H), 1.53-1.4 (m, 1H).

1. customto produce a pale yellow solid
2. customTHF was removed in vacuo
3. dissolutionthe residue was dissolved in ether (500 mL)
4. extractionextracted with 10% HCl (4×150 mL)
5. extractionThe aqueous acidic phase was back extracted with ether/ethyl acetate (75 mL/25 mL)
6. additionneutralized to pH 7 by the addition of sodium bicarbonate cautiously in small portions
7. additionby adding a few drops of 10N NaOH
8. extractionextracted with dichlormethane (5×200 mL)
9. dry with materialdried over anhydrous sodium sulfate
10. concentrationconcentrated
11. customPurification by flash column chromatrography

ORD-Eintrag

ord-d258b7afb4dd4ffaa233c4f6948e3024

Quelldatensatz

uspto-grants-1993_03

DOI

10.6084/m9.figshare.5104873.v1

Patentnummer

US05194605