2-Mercaptoethanol → Ristianol

HRID 1389784Notes

Reaction equation

HRID 1389784 reaction equation
C[O-].[Na+].Cl.[N:5]1[CH:10]=[CH:9][C:8]([CH2:11]Cl)=[CH:7][CH:6]=1.[SH:13][CH2:14][CH2:15][OH:16]>C(O)C>[OH:16][CH2:15][CH2:14][S:13][CH2:11][C:8]1[CH:9]=[CH:10][N:5]=[CH:6][CH:7]=1

Participants

5

Reactant 3

HCID 15672-MercaptoethanolHCID 745704-(Chloromethyl)pyridinium chlorideHCID 10942334Sodium Methoxide

Product 1

HCID 54050Ristianol

Reagents, catalysts & solvents 1

HCID 702EthanolSolvent2×

Procedure

Under a nitrogen atmosphere, sodium methoxide (170.1 g., 3.15 moles, 2.1 equiv.) was dissolved in 2.7 l. of absolute ethanol, and the stirred solution cooled in an ice bath. Solid 4-picolyl chloride hydrochloride (97%, 253.6 g., 1.5 moles, 1 equiv.) was added portionwise over approximately 15 minutes. A solution of 2-mercaptoethanol (128.9 g., 1.65 moles), dissolved in 300 ml. of ethanol, was then added dropwise over approximately 30 minutes. The reaction was allowed to warm to room temperature and stirred for 21.5 hours. Diatomaceous earth was added to the reaction mixture, which after brief stirring, was filtered. The filter cake was repulped 2×1500 ml. of absolute ethanol, the filtrates were combined with the original filtrate, and the combined ethanol solution evaporated to a solid-containing oil (approximately 290 g.). The oil was dissolved in 1500 ml. of hot chloroform, treated with activated carbon, filtered, reconcentrated to oil (274 g.) and chromatographed on 1.5 kg. of silcia gel in a 10 cm. diameter column using chloroform as eluant. Fractions of approximately 3.5 l. were taken. Fractions 3 to 18 were combined, concentrated to oil, taken up in approximately 1 l. of ethyl acetate and evaporated to yield relatively pure 4-(2-hydroxyethylthiomethyl)pyridine [195.7 g., ir (film): 3.17, 3.51, 3.58, 6.27, 9.45 and 12.27μ; pnmr/CDCl3 /TMS/δ: 8.63-8.42 (m, 2H), 7.38-7.18 (m, 2H), 3.73 (t, 2H), 3.72 (s, 2H), 2.98 (s, broad, 1H) and 2.63 (t, 2H) ppm]. On standing, product prepared by this procedure slowly crystallized (m.p. 47°-48° C.).

Workup

  1. additionDiatomaceous earth was added to the reaction mixture, which after brief stirring
  2. filtrationwas filtered
  3. customthe combined ethanol solution evaporated to a solid-containing oil (approximately 290 g.)
  4. dissolutionThe oil was dissolved in 1500 ml
  5. additionof hot chloroform, treated with activated carbon
  6. filtrationfiltered
  7. customchromatographed on 1.5 kg
  8. concentrationconcentrated to oil
  9. customof ethyl acetate and evaporated

Sources & evidence

ORD record
ord-ba09e706c76c45fa872ac4fba3d3e0b9
Source dataset
uspto-grants-1981_01
Patent number
US04246263

Reaction notes

Loading…