Sulfuric Acid → HCID 67485983, compound

HRID 534062Notes

Reaction equation

HRID 534062 reaction equation
[CH3:1][C:2]1[C:7]([O:8][C:9]2[C:10]([C:22]#[N:23])=[N:11][CH:12]=[C:13]([S:15][C:16]3[CH:21]=[CH:20][CH:19]=[CH:18][N:17]=3)[CH:14]=2)=[CH:6][CH:5]=[CH:4][N:3]=1.[OH:24]S(O)(=O)=O>>[CH3:1][C:2]1[C:7]([O:8][C:9]2[C:10]([C:22]([NH2:23])=[O:24])=[N:11][CH:12]=[C:13]([S:15][C:16]3[CH:21]=[CH:20][CH:19]=[CH:18][N:17]=3)[CH:14]=2)=[CH:6][CH:5]=[CH:4][N:3]=1

Participants

3

Reactant 2

HCID 1118Sulfuric AcidHCID 67485792HCID 67485792, compound

Product 1

HCID 67485983HCID 67485983, compoundYield 96%

Conditions

Temperature
50 °C

Procedure

To concentrated H2SO4 (90 mL) cooled with an ice bath was added 3-(2-methylpyridin-3-yloxy)-5-(pyridin-2-ylthio)picolinonitrile (43 g, 130 mmol) in portions such that the internal temperature did not exceed 50° C. but did not go below 25° C. After complete addition, the mixture was stirred in the ice bath until the reaction started to cool, at which point the reaction was removed from the ice bath and the mixture was heated to 50° C. The reaction was cooled to ambient temperature and slowly added to ice water over 3 minutes (about 1400 mL of 30% ice in water). The mixture was further cooled in an ice bath to 5° C. The mixture was neutralized to pH˜10 with 4M NaOH (about 800 mL) such that the internal temperature did not exceed 20° C., at which point a solid formed. The mixture was stirred for 20 minutes, then filtered and washed with MTBE (5×150 mL), hexanes (5×100 mL), and dried at under vacuum to afford 3-(2-methylpyridin-3-yloxy)-5-(pyridin-2-ylthio)picolinamide (43 g, 96%).

Workup

  1. customdid not exceed 50° C.
  2. customdid not go below 25° C
  3. additionAfter complete addition
  4. temperatureto cool, at which
  5. customwas removed from the ice bath
  6. temperatureThe reaction was cooled to ambient temperature
  7. additionslowly added to ice water over 3 minutes (about 1400 mL of 30% ice in water)
  8. temperatureThe mixture was further cooled in an ice bath to 5° C
  9. customdid not exceed 20° C., at which point
  10. customformed
  11. filtrationfiltered
  12. washwashed with MTBE (5×150 mL), hexanes (5×100 mL)
  13. customdried at under vacuum

Sources & evidence

ORD record
ord-01c8d8e2307f48b6951593e638684a03
Source dataset
uspto-grants-2014_10
Patent number
US08853409B2

Reaction notes

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