Water → 6-Methoxy-2-(Phenylmethylthio)-3-Pyridinecarboxylic Acid, Methyl Ester

HRID 1029336Notes

Reaction equation

HRID 1029336 reaction equation
[H-].[Na+].[CH2:3]([SH:10])[C:4]1[CH:9]=[CH:8][CH:7]=[CH:6][CH:5]=1.F[C:12]1[C:17]([C:18]([O:20][CH3:21])=[O:19])=[CH:16][CH:15]=[C:14]([O:22][CH3:23])[N:13]=1.O>CN(C)C=O>[CH3:23][O:22][C:14]1[N:13]=[C:12]([S:10][CH2:3][C:4]2[CH:9]=[CH:8][CH:7]=[CH:6][CH:5]=2)[C:17]([C:18]([O:20][CH3:21])=[O:19])=[CH:16][CH:15]=1

Participants

6

Reactant 4

HCID 962WaterHCID 7509Benzyl mercaptanHCID 24758Sodium hydrideHCID 10821376Methyl 2-fluoro-6-methoxynicotinate

Product 1

HCID 143719726-Methoxy-2-(Phenylmethylthio)-3-Pyridinecarboxylic Acid, Methyl EsterYield 70.5%

Reagents, catalysts & solvents 1

HCID 6228DimethylformamideSolvent

Procedure

To a stirred mixture of 0.8 g (0.0161 mol) of 50% sodium hydride (in mineral oil), which had been washed with hexanes, in 20 mL dry dimethylformamide cooled to -5° under nitrogen was added dropwise 1.9 mL (0.0161 mol) benzyl mercaptan The suspension was stirred at room temperature for 1 hour, cooled to 0°, and a solution of 3.2 g (0.0147 mol) of the product of Example 13 in 20 mL dry dimethylformamide was added dropwise. After warming to room temperature, the solution was poured into water and extracted with ether. The combined organic layers were washed with water and with brine, dried over magnesium sulfate, and evaporated to an oil which was purified by flash chromatography to afford 3.0 g (64%) of a yellow solid: m.p. 67°-71°; NMR (CDCl3, 200 MHz) 3.88 (3H, s), 3.96 (3H, s), 4.46 (2H, s), 6.44 (1H, d, J=9Hz), 7.2-7.5 (5H, m), 8.1 (1H, d, J=9Hz); IR (nujol) 1700, 1580, 1305, 1255 cm-1.

Workup

  1. washhad been washed with hexanes, in 20 mL dry dimethylformamide
  2. temperaturecooled to -5° under nitrogen
  3. temperaturecooled to 0°
  4. temperatureAfter warming to room temperature
  5. extractionextracted with ether
  6. washThe combined organic layers were washed with water and with brine
  7. dry with materialdried over magnesium sulfate
  8. customevaporated to an oil which
  9. customwas purified by flash chromatography

Sources & evidence

ORD record
ord-719958ab32cd40028a9ea9fd56efea71
Source dataset
uspto-grants-1992_04
Patent number
US05102444

Reaction notes

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