p-Toluenesulfonic acid → 2-(Pyrid-3-yl)-1,3-oxathiane

HRID 1701910Notes

Reaction equation

HRID 1701910 reaction equation
N1C=CC=C(C=O)C=1.SCCCO.C1(C)C=CC(S(O)(=O)=O)=CC=1.CNC([C:29]1([C:35]2[CH:36]=[N:37][CH:38]=[CH:39][CH:40]=2)[S:34][CH2:33][CH2:32][CH2:31][O:30]1)=S>ClCCCl>[N:37]1[CH:38]=[CH:39][CH:40]=[C:35]([CH:29]2[S:34][CH2:33][CH2:32][CH2:31][O:30]2)[CH:36]=1

Participants

6

Reactant 4

HCID 6101p-Toluenesulfonic acidHCID 103713-PyridinecarboxaldehydeHCID 882113-MercaptopropanolHCID 10467514HCID 10467514, compound

Product 1

HCID 100352402-(Pyrid-3-yl)-1,3-oxathiane

Reagents, catalysts & solvents 1

HCID 111,2-DichloroethaneSolvent

Conditions

Temperature
20 °C

Procedure

A solution of pyridine-3-carboxaldehyde (16 g), 3-mercaptopropan-1-ol (48 g) and para-toluenesulphonic acid (2.25 g) in 1,2-dichloroethane (1500 cc) is kept at the boil for 15 hours so that the water formed is removed by azeotropic distillation. After cooling to a temperature of about 20° C., the reaction mixture is washed three times with a 5 N aqueous solution of sodium hydroxide (750 cc in total) and then three times with distilled water (1500 cc in total). The organic phase is dried over anhydrous sodium sulphate and filtered, and the filtrate is concentrated to dryness under reduced pressure (20 mm Hg; 2.7 kPa) at 50° C. The product obtained (15.6 g) is chromatographed in neutral silica gel (200 g) contained in a column of diameter 3.7 cm. Elution is carried out successively with a cyclohexane/ethyl acetate mixture (80/20 by volume; 600 cc) and a cyclohexane/ethyl acetate mixture (70/30 by volume; 2700 cc), 300 cc fractions being collected. Fractions 5 to 11 are combined and concentrated to dryness under reduced pressure (20 mm Hg; 2.7 kPa) at 50° C. 2-(Pyrid-3-yl)-1,3-oxathiane (8.6 g) is thus obtained in the form of a yellow oil.

Workup

  1. customformed
  2. customis removed by azeotropic distillation
  3. washthe reaction mixture is washed three times with a 5 N aqueous solution of sodium hydroxide (750 cc in total)
  4. dry with materialThe organic phase is dried over anhydrous sodium sulphate
  5. filtrationfiltered
  6. concentrationthe filtrate is concentrated to dryness under reduced pressure (20 mm Hg; 2.7 kPa) at 50° C
  7. customThe product obtained (15.6 g)
  8. customis chromatographed in neutral silica gel (200 g)
  9. washElution
  10. customa cyclohexane/ethyl acetate mixture (70/30 by volume; 2700 cc), 300 cc fractions being collected
  11. concentrationconcentrated to dryness under reduced pressure (20 mm Hg; 2.7 kPa) at 50° C

Sources & evidence

ORD record
ord-0fe7be066a5541799325eacb458c67fd
Source dataset
uspto-grants-1983_04
Patent number
US04379154

Reaction notes

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