3-Methylpyridine → Cyantraniliprole

HRID 404830Notes

Reaction equation

HRID 404830 reaction equation
[Br:1][C:2]1[CH:6]=[C:5]([C:7]([OH:9])=O)[N:4]([C:10]2[C:15]([Cl:16])=[CH:14][CH:13]=[CH:12][N:11]=2)[N:3]=1.[NH2:17][C:18]1[C:27]([CH3:28])=[CH:26][C:25]([C:29]#[N:30])=[CH:24][C:19]=1[C:20]([NH:22][CH3:23])=[O:21].N1C=CC=C(C)C=1.CS(Cl)(=O)=O>C(#N)C.O>[Br:1][C:2]1[CH:6]=[C:5]([C:7]([NH:17][C:18]2[C:19]([C:20]([NH:22][CH3:23])=[O:21])=[CH:24][C:25]([C:29]#[N:30])=[CH:26][C:27]=2[CH3:28])=[O:9])[N:4]([C:10]2[C:15]([Cl:16])=[CH:14][CH:13]=[CH:12][N:11]=2)[N:3]=1

Participants

7

Reactant 4

HCID 79703-MethylpyridineHCID 31297Methanesulfonyl chlorideHCID 115875353-Bromo-1-(3-chloropyridin-2-yl)-1H-pyrazole-5-carboxylic acidHCID 251572822-Amino-5-cyano-N,3-dimethylbenzamide

Product 1

HCID 11578610Cyantraniliprole

Reagents, catalysts & solvents 2

HCID 962WaterSolvent2×HCID 6342AcetonitrileSolvent

Conditions

Temperature
17.5 °C

Procedure

To a mixture of 3-bromo-1-(3-chloro-2-pyridinyl)-1H-pyrazole-5-carboxylic acid (see PCT Patent Publication WO 2003/015519 for a method of preparation) (97.4% purity, 15.4 g, 49.6 mmol) and 2-amino-5-cyano-N,3-dimethylbenzamide (10.0 g, 52.5 mmol) in acetonitrile (80 mL) was added 3-picoline (13.9 g, 148 mmol). The mixture was cooled to 15 to 20° C., and then methanesulfonyl chloride (8.2 g, 71.2 mmol) was added dropwise at 15 to 20° C. After 1 h, water (37.3 g) was added dropwise to the reaction mixture while maintaining the temperature at 15 to 20° C. After the addition was complete, the mixture was heated at 45 to 50° C. for 30 minutes, and then cooled to 15 to 25° C. for 1 h. The mixture was filtered and the solids collected were washed with acetonitrile-water (approximately a 5:1 mixture, 2×10 mL) and acetonitrile (2×10 mL), and then dried under nitrogen to afford 24.0 g (93.6% corrected yield based on an assay of 91.6%, with a water content of 6%) of the title compound as an off-white solid.

Workup

  1. temperaturewhile maintaining the temperature at 15 to 20° C
  2. additionAfter the addition
  3. temperaturethe mixture was heated at 45 to 50° C. for 30 minutes
  4. temperaturecooled to 15 to 25° C. for 1 h
  5. filtrationThe mixture was filtered
  6. customthe solids collected
  7. washwere washed with acetonitrile-water (approximately a 5:1 mixture, 2×10 mL) and acetonitrile (2×10 mL)
  8. customdried under nitrogen
  9. customto afford 24.0 g (93.6%
  10. customcorrected yield

Sources & evidence

ORD record
ord-75d5e9a1e4244cfbb24c32b6cc146d84
Source dataset
uspto-grants-2014_06
Patent number
US08748630B2

Reaction notes

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