2-Propanethiol → HCID 13102677, compound

HRID 1757993Notes

Reaction equation

HRID 1757993 reaction equation
CC([O-])(C)C.[K+].CC(S)C.[CH3:11][CH:12]([S:14][C:15]1[C:16](C(O)=O)=[N:17][C:18]([S:21][CH:22]([CH3:24])[CH3:23])=[CH:19][CH:20]=1)[CH3:13]>CN(C=O)C>[CH3:24][CH:22]([S:21][C:18]1[CH:19]=[CH:20][C:15]([S:14][CH:12]([CH3:13])[CH3:11])=[CH:16][N:17]=1)[CH3:23]

Participants

5

Reactant 3

HCID 63642-PropanethiolHCID 13278014HCID 13278014, compoundHCID 23665647Potassium tert-butoxide

Product 1

HCID 13102677HCID 13102677, compound

Reagents, catalysts & solvents 1

HCID 6228DimethylformamideSolvent

Conditions

Temperature
50 °C

Procedure

To 198 g of t-BuOK dissolved in 300 ml of DMF was added 2-propanethiol (163.47 ml) dropwise with an ice bath employed to keep the temperature below 50° C. As salt began to precipitate out an additional 50 ml of DMF was added. After addition was complete, the ice bath was removed and the mixture heated to 50° C. A solution of 100 g of methyl 3,6-dichloro-pyridine-2-carboxylate dissolved in DMF was added and the temperature during addition rose to 115° C. The temperature was then maintained at approximately 105°-110° C. until addition was completed and then the resulting mixture was heated at 100°-110° C. for 11/2 hrs. The reaction mixture was allowed to cool and the solvent removed in a rotary evaporator. The brown residue which remained was washed with ether and then dissolved in water. The solution was acidified with HCl, and the product, which oiled out, extracted with CH2Cl2. The CH2Cl2 was then removed using a rotary evaporator. Infrared spectroscopy (IR) and nuclear magnetic resonance spectroscopy (NMR) indicated that 3,6-bis((1-methylethyl)thio)-2-pyridinecarboxylic acid had formed. The 3,6-bis((1-methylethyl)thio)-2-pyridinecarboxylic acid was decarboxylated employing a Kugelrohr distillation apparatus, and 2,5-bis((1-methylethyl)thio)pyridine obtained, b.p. 310° C. (760 mm Hg).

Workup

  1. customthe temperature below 50° C
  2. customto precipitate out an additional 50 ml of DMF
  3. additionwas added
  4. additionAfter addition
  5. customthe ice bath was removed
  6. dissolutionA solution of 100 g of methyl 3,6-dichloro-pyridine-2-carboxylate dissolved in DMF
  7. additionwas added
  8. additionthe temperature during addition
  9. customrose to 115° C
  10. temperatureThe temperature was then maintained at approximately 105°-110° C. until addition
  11. temperaturethe resulting mixture was heated at 100°-110° C. for 11/2 hrs
  12. temperatureto cool
  13. customthe solvent removed in a rotary evaporator
  14. washThe brown residue which remained was washed with ether
  15. dissolutiondissolved in water
  16. extractionextracted with CH2Cl2
  17. customThe CH2Cl2 was then removed
  18. customa rotary evaporator
  19. customhad formed
  20. distillationa Kugelrohr distillation apparatus, and 2,5-bis((1-methylethyl)thio)pyridine
  21. customobtained

Sources & evidence

ORD record
ord-dd78b91872e24621a320c6e3fdade016
Source dataset
uspto-grants-1983_02
Patent number
US04371537

Reaction notes

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