Diphenyl Ether → 2,3-Bis(methylsulfanyl)pyridine

HRID 2290398Notes

Reaction equation

HRID 2290398 reaction equation
C1(OC2C=CC=CC=2)C=CC=CC=1.ClC1C=CC(C(O)=O)=NC=1SC.[CH3:26][S:27][C:28]1[CH:29]=[CH:30][C:31](C(O)=O)=[N:32][C:33]=1[S:34][CH3:35]>C1(C)C(C)=CC=CC=1>[CH3:35][S:34][C:33]1[C:28]([S:27][CH3:26])=[CH:29][CH:30]=[CH:31][N:32]=1

Participants

4

Reactant 2

HCID 7583Diphenyl EtherHCID 86741067HCID 86741067, compound

Product 1

HCID 3316602,3-Bis(methylsulfanyl)pyridine

Reagents, catalysts & solvents 1

HCID 7237O-XyleneSolvent

Conditions

Temperature
100 °C

Procedure

A stirred solution of 250 ml of diphenyl oxide was heated to 200° C. A 54 g quantity of the 5-chloro-6-(methylthio)-2-pyridinecarboxylic acid/5,6-bis(methylthio)-2-pyridinecarboxylic acid mixture described above was added portionwise as a solid. The mixture was stirred for 1 hour with the temperature being maintained below 235° C. The mixture was cooled to 100° C., diluted with xylene and cooled to room temperature, then extracted three times with 75 ml of 6N HCl. The combined aqueous fractions were back-washed with diethyl ether, then stirred with CH2Cl2 and made strongly basic with 25% NaOH. The organic layer was separated, washed with water, then brine, and dried (Na2SO4). The solids were removed from the organic layer by filtration, then the filtrate was evaporated leaving a brown oil which was purified on a Kugelrohr distillation apparatus and 23.6 g of an oil obtained. The components of the oil were separated employing high pressure liquid chromatography (Porasil, 3% diethyl ether/hexane) and 19.42 g of 2,3-bis(methylthio)pyridine (b.p. 85° C. at 0.3 mm Hg) and 0.77 g of 3-chloro-2-(methylthio)pyridine (b.p. 80° C. at 0.3 mm Hg) obtained, both as colorless oils.

Workup

  1. temperaturebeing maintained below 235° C
  2. temperaturecooled to room temperature
  3. extractionextracted three times with 75 ml of 6N HCl
  4. washThe combined aqueous fractions were back-washed with diethyl ether
  5. stirringstirred with CH2Cl2
  6. customThe organic layer was separated
  7. washwashed with water
  8. dry with materialbrine, and dried (Na2SO4)
  9. customThe solids were removed from the organic layer by filtration
  10. customthe filtrate was evaporated
  11. customleaving a brown oil which
  12. distillationwas purified on a Kugelrohr distillation apparatus and 23.6 g of an oil
  13. customobtained
  14. customThe components of the oil were separated
  15. customobtained

Sources & evidence

ORD record
ord-6258b49087b94360ba64c040acaa0bee
Source dataset
uspto-grants-1986_10
Patent number
US04616087

Reaction notes

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