Water → HCID 13711415, compound

HRID 2118721Notes

Reaction equation

HRID 2118721 reaction equation
[CH3:1][C:2]1[N:7]=[C:6]([CH:8]=O)[CH:5]=[CH:4][CH:3]=1.[CH2:10]([SH:14])[CH2:11][CH2:12][SH:13].C1(C)C=CC(S(O)(=O)=O)=CC=1.O>C1(C)C=CC=CC=1>[CH3:1][C:2]1[N:7]=[C:6]([CH:8]2[S:14][CH2:10][CH2:11][CH2:12][S:13]2)[CH:5]=[CH:4][CH:3]=1

Participants

6

Reactant 4

HCID 962WaterHCID 6101p-Toluenesulfonic acidHCID 80131,3-PropanedithiolHCID 707376-Methyl-2-pyridinecarboxaldehyde

Product 1

HCID 13711415HCID 13711415, compoundYield 51.7%

Reagents, catalysts & solvents 1

HCID 1140TolueneSolvent

Conditions

Temperature
20 °C

Procedure

A solution of 6-methyl-2-pyridinecarboxaldehyde (100 g), 1,3-propanedithiol (285 g) and para-toluenesulphonic acid (11.8 g) in toluene (2.6 liters) is heated to boiling for 12 hours 40 minutes, the water formed being removed by azeotropic distillation. After being cooled to a temperature in the region of 20° C., the reaction mixture is poured into a mixture of distilled water (1 liter) and ice (500 g), and approximately 10N aqueous potassium hydroxide solution is then added dropwise. After decantation, the organic solution is washed with approximately 5N aqueous potassium hydroxide solution, and 3 times with distilled water (1700 cc in total), dried over anhydrous magnesium sulphate and concentrated to dryness under reduced pressure (25 mm Hg; 3.25 kPa) at 50° C. The product obtained (160.2 g) is chromatographed on neutral silica gel (980 g; 0.063-0.200 mm) contained in a column 8 cm in diameter. The product is eluted with a mixture of cyclohexane and ethyl acetate (70:30 by volume), collecting 300-cc fractions. Fractions 9 to 23 are combined and concentrated to dryness under reduced pressure (25 mm Hg; 3.25 kPa) at 50° C. 2-(6-Methyl-2-pyridyl)-1,3-dithiane (90.2 g), m.p. 74° C., is thereby obtained.

Workup

  1. custombeing removed by azeotropic distillation
  2. additionthe reaction mixture is poured into a mixture of distilled water (1 liter) and ice (500 g), and approximately 10N aqueous potassium hydroxide solution
  3. additionis then added dropwise
  4. washAfter decantation, the organic solution is washed with approximately 5N aqueous potassium hydroxide solution, and 3 times with distilled water (1700 cc in total)
  5. dry with materialdried over anhydrous magnesium sulphate
  6. concentrationconcentrated to dryness under reduced pressure (25 mm Hg; 3.25 kPa) at 50° C
  7. customThe product obtained (160.2 g)
  8. customis chromatographed on neutral silica gel (980 g; 0.063-0.200 mm)
  9. washThe product is eluted with a mixture of cyclohexane and ethyl acetate (70:30 by volume)
  10. customcollecting 300-cc fractions
  11. concentrationconcentrated to dryness under reduced pressure (25 mm Hg; 3.25 kPa) at 50° C

Sources & evidence

ORD record
ord-ad9bd19a9254491e81372fcb9adbc1c3
Source dataset
uspto-grants-1987_07
Patent number
US04680303

Reaction notes

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