m-Chloroperbenzoic acid → Pyridine, 3-[[(4-chlorobutyl)sulfinyl]methyl]-

HRID 1589153Notes

Reaction equation

HRID 1589153 reaction equation
ClC1C=CC=C(C(OO)=[O:9])C=1.[N:12]1[CH:17]=[CH:16][CH:15]=[C:14]([CH2:18][S:19][CH2:20][CH2:21][CH2:22][CH2:23][Cl:24])[CH:13]=1.C(=O)(O)[O-].[Na+]>C(Cl)Cl>[Cl:24][CH2:23][CH2:22][CH2:21][CH2:20][S:19]([CH2:18][C:14]1[CH:13]=[N:12][CH:17]=[CH:16][CH:15]=1)=[O:9]

Participants

5

Reactant 3

HCID 70297m-Chloroperbenzoic acidHCID 516892Sodium BicarbonateHCID 10443278Pyridine, 3-[[(4-chlorobutyl)thio]methyl]-

Product 1

HCID 10443914Pyridine, 3-[[(4-chlorobutyl)sulfinyl]methyl]-Yield 23%

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent2×

Procedure

A solution of 85% pure m-chloroperbenzoic acid (107 g) in methylene chloride (900 cc) is added dropwise, in the course of 1 hour 30 minutes, at a temperature of about 20° C., to a solution of 4-chlorobutyl pyridin-3-yl-methyl sulphide (103 g) in methylene chloride (900 cc). After stirring for 17 hours at the same temperature, a 10% (by weight) aqueous solution of sodium bicarbonate (3 liters) is added slowly. The organic solution is decanted and then washed with a 10% solution of sodium bicarbonate (1 liter). The aqueous phases are combined and extracted with methylene chloride (500 cc). The organic extracts are combined and washed twice with distilled water (2 liters in total), dried over anhydrous sodium sulphate and concentrated to dryness under reduced pressure (25 mm Hg; 3.4 kPa) at 35° C. The product obtained (87 g) is chromatographed on neutral silica gel (400 g) contained in a column of diameter 4.7 cm. Elution is carried out with methylene chloride (10 liters), three 1 liter fractions, ten 100 cc fractions and twelve 500 cc fractions being collected successively. Fractions 11 to 25 are combined and concentrated to dryness under reduced pressure (25 mm Hg; 3.4 kPa) at 35° C. to give 3-(4-chlorobutyl)sulphinylmethylpyridine (25.4 g) in the form of an orange oil [Rf=0.22; chromatography on a thin layer of silica gel; solvent: ethyl acetate/methanol (80/20 by volume)].

Workup

  1. customThe organic solution is decanted
  2. washwashed with a 10% solution of sodium bicarbonate (1 liter)
  3. extractionextracted with methylene chloride (500 cc)
  4. washwashed twice with distilled water (2 liters in total)
  5. dry with materialdried over anhydrous sodium sulphate
  6. concentrationconcentrated to dryness under reduced pressure (25 mm Hg; 3.4 kPa) at 35° C
  7. customThe product obtained (87 g)
  8. customis chromatographed on neutral silica gel (400 g)
  9. washElution
  10. custombeing collected successively
  11. concentrationconcentrated to dryness under reduced pressure (25 mm Hg; 3.4 kPa) at 35° C.

Sources & evidence

ORD record
ord-cf711ec350194cbb927cadf4f80bfa58
Source dataset
uspto-grants-1986_02
Patent number
US04568682

Reaction notes

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