Hydrogen Sulfide → HCID 13825493, compound

HRID 1905836Notes

Reaction equation

HRID 1905836 reaction equation
C[CH:2]([NH:10][C:11]1[C:16]([CH3:17])=[CH:15][CH:14]=[CH:13][CH:12]=1)[C:3]([NH:5][NH:6][C:7](=O)[CH3:8])=O.P12(SP3(SP(SP(S3)(S1)=S)(=S)S2)=S)=S.[SH2:32].N1C=CC=C[CH:34]=1>ClCCl>[CH3:34][C:12]1[CH:13]=[CH:14][CH:15]=[C:16]([CH3:17])[C:11]=1[NH:10][CH2:2][C:3]1[S:32][C:7]([CH3:8])=[N:6][N:5]=1

Participants

6

Reactant 4

HCID 402Hydrogen SulfideHCID 1049PyridineHCID 14817Phosphorus sulfide (P2S5)HCID 70426821HCID 70426821, compound

Product 1

HCID 13825493HCID 13825493, compound

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent

Procedure

To a stirred solution of 16.0 g (0.068 mol) 1-(2,6-dimethylphenylaminoacetyl)-2-acetylhydrazine in 150 ml pyridine was added 15.1 g (0.068 mol) phosphorus pentasulfide in small portions. A mild exotherm ensued. The reaction mixture was heated to 140°-150° C. when an exotherm ensued. The reaction temperature rose to 170° C., and then subsided. Hydrogen sulfide was liberated. The reaction was kept at 140°-150° C. for 2 hours and then at 25° C. for about 16 hours. The pyridine solution was decanted from a gummy brown residue. The residue was extracted with dichloromethane. The dichloromethane extracts were combined with the pyridine solution and evaporated under reduced pressure to give an oil. The oil was dissolved in dichloromethane and treated with ice water to destroy a small amount of unreacted phosphorus pentasulfide. The dichloromethane solution was then washed with cold dilute aqueous sodium hydroxide solution, water, dried over magnesium sulfate, filtered and evaporated under reduced pressure at 40°-50° C. to give an oil. The oil was column chromatographed on 200 g silica gel using petroleum ether/diethyl ether as eluants. The major fractions were combined in dichloromethane, dried over magnesium sulfate, filtered and evaporated under reduced pressure to give a clear oil which crystallized upon trituration with petroleum ether to give 11.6 g of 2-(2,6-dimethylphenylaminomethyl)-5-methyl-1,3,4-thiadiazole, m.p. 68°-69° C. The product is tabulated in Table I as Compound No. 29A.

Workup

  1. temperatureThe reaction mixture was heated to 140°-150° C. when an exotherm
  2. customrose to 170° C.
  3. waitat 25° C. for about 16 hours
  4. customThe pyridine solution was decanted from a gummy brown residue
  5. extractionThe residue was extracted with dichloromethane
  6. customevaporated under reduced pressure
  7. customto give an oil
  8. customto destroy a small amount of unreacted phosphorus pentasulfide
  9. washThe dichloromethane solution was then washed with cold dilute aqueous sodium hydroxide solution, water
  10. dry with materialdried over magnesium sulfate
  11. filtrationfiltered
  12. customevaporated under reduced pressure at 40°-50° C.
  13. customto give an oil
  14. customchromatographed on 200 g silica gel
  15. dry with materialdried over magnesium sulfate
  16. filtrationfiltered
  17. customevaporated under reduced pressure
  18. customto give a clear oil which
  19. customcrystallized upon trituration with petroleum ether

Sources & evidence

ORD record
ord-4bd8349fd26944278f9b88616b6b3f12
Source dataset
uspto-grants-1987_03
Patent number
US04648897

Reaction notes

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