Water → (1R,2R)-2-(3-pyridyl)tetrahydro-2H-thiopyran 1-oxide

A stirred solution of (R)-6-(3-pyridyl)-3,4-dihydro-2H-thiopyran 1-oxide (22.43 g;88.2%ee) in ethanol (227 ml) is treated, portionwise, with sodium borohydride powder (3.52 g) under nitrogen at room temperature, and the mixture is stirred for 2.5 hours. It is then treated with a further quantity of sodium borohydride (0.43 g), and the mixture is stirred for a further period of 15 minutes. The mixture is treated with water (454 ml) and extracted with dichloromethane (2×340 ml). The combined extracts are washed with water 340 ml), dried over magnesium sulphate and the solvent is removed by evaporation under reduced pressure, to give an oily paste (18.1 g). This paste is treated with ethyl acetate (72 ml) and the mixture is heated at reflux, with stirring. The solution is allowed to cool to room temperature, and stirred for 3 hours. The resulting suspension is cooled to 0° C. for 1 hour, and then filtered. The pale yellow solid is washed with a little cold ethyl acetate and sucked dry using vacuum filtration, to give (1R,2R)-2-(3-pyridyl)tetrahydro-2H-thiopyran 1 -oxide (8.03 g;99.7%ee), m.p. 124.5°-126.50° C. [Elemental analysis:- C,61.2;H,6.67; N,7.1 ;S,16.7%. Calculated:- C,61.51 ;H,6.71 ;N,7.17; S,16.42%. NMR (CDCl3):- 1.6(m,1H), 8(m,2H),2.0(m,1H),2.4(m,1H),2.7(m,2H),3.2(m,1H), 3.5(dd,1H),7.3(m,1H),7.7(dt,1H),8.6(m,2H)].

1. extractionextracted with dichloromethane (2×340 ml)
2. washThe combined extracts are washed with water 340 ml),
3. dry with materialdried over magnesium sulphate
4. customthe solvent is removed by evaporation under reduced pressure
5. customto give an oily paste (18.1 g)
6. temperaturethe mixture is heated
7. temperatureat reflux
8. stirringwith stirring
9. stirringstirred for 3 hours
10. temperatureThe resulting suspension is cooled to 0° C. for 1 hour
11. filtrationfiltered
12. washThe pale yellow solid is washed with a little cold ethyl acetate
13. customsucked dry
14. filtrationvacuum filtration

ORD record

ord-17e1fe083bc541e8bb186e38fddc2b26

Source dataset

uspto-grants-1998_07

DOI

10.6084/m9.figshare.5104873.v1

Patent number

US05780636