Chloride → Ethyl {[(pyridin-4-yl)methyl]sulfanyl}acetate

HRID 1758085Notes

Reaction equation

HRID 1758085 reaction equation
[Na].[O-]CC.[Na+].Cl.[N:7]1[CH:12]=[CH:11][C:10]([CH2:13]Cl)=[CH:9][CH:8]=1.[SH:15][CH2:16][C:17]([O:19][CH2:20][CH3:21])=[O:18].[Cl-]>C(O)C>[N:7]1[CH:12]=[CH:11][C:10]([CH2:13][S:15][CH2:16][C:17]([O:19][CH2:20][CH3:21])=[O:18])=[CH:9][CH:8]=1

Participants

7

Reactant 5

HCID 312Chloride2×HCID 12185Ethyl ThioglycolateHCID 745704-(Chloromethyl)pyridinium chlorideHCID 2723922Sodium ethoxideHCID 5360545Sodium

Product 1

HCID 14625126Ethyl {[(pyridin-4-yl)methyl]sulfanyl}acetateYield 77.6%

Reagents, catalysts & solvents 1

HCID 702EthanolSolvent3×

Procedure

Under nitrogen, absolute ethanol (120 ml.) was warmed to 40° C. Sodium metal (5.18 g., 0.225 mole) was added portionwise at such a rate as to maintain gentle reflux. After one hour, the resulting clear solution of sodium ethoxide was cooled in an ice-water bath. 4-Picolyl chloride hydrochloride (16.4 g., 0.10 mole) was slurried in 60 ml. of ethanol and ethyl mercaptoacetate (13.2 g., 0.11 mole) in 30 ml. of ethanol were placed in separate additional funnels. After 10% of the organic chloride was added, the remaining chloride and the mercaptan were added simultaneously and dropwise. The reaction mixture was warmed to room temperature, stirred for 16 hours and filtered over diatomaceous earth with ethanol wash. The combined filtrate and wash was evaporated to an oil (26 g.). The oil was chromatographed on 500 g. of silica gel, eluting with chloroform and monitoring by tlc. Clean fractions were combined and evaporated to yield title product as an oil [16.4 g.; Rf (9:1 chloroform:methanol) 0.75; ir (film) 3390, 2976, 1730, 1600, 1410, 1280, 1160, 1120, 1030, 813, 750 cm-1 ].

Workup

  1. temperatureto maintain gentle reflux
  2. filtrationfiltered over diatomaceous earth with ethanol
  3. washwash
  4. washThe combined filtrate and wash
  5. customwas evaporated to an oil (26 g.)
  6. customThe oil was chromatographed on 500 g
  7. washof silica gel, eluting with chloroform and monitoring by tlc
  8. customevaporated

Sources & evidence

ORD record
ord-2c14f996724c495bb08d975ac7911dd9
Source dataset
uspto-grants-1983_02
Patent number
US04371696

Reaction notes

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