Sulfuric Acid → HCID 67485983, compound

HRID 534134Notes

Reaction equation

HRID 534134 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 added to ice water slowly over 3 minutes (about 1400 mL of 30% ice in water). The mixture was further cooled in an ice bath to 5° C. and neutralized to about pH 10 with 4M NaOH (about 800 mL) at a rate 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. additionadded to ice water slowly over 3 minutes (about 1400 mL of 30% ice in water)
  8. temperatureThe mixture was further cooled in an ice bath to 5° C. and neutralized to about pH 10 with 4M NaOH (about 800 mL) at a rate such that the internal temperature
  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-bde3653cc8aa4f40956e2e989c6d6358
Source dataset
uspto-grants-2014_10
Patent number
US08853409B2

Reaction notes

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