Hydrochloric Acid → Cyantraniliprole

HRID 490983Notes

Reaction equation

HRID 490983 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.Cl>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

8

Reactant 5

HCID 313Hydrochloric AcidHCID 79703-MethylpyridineHCID 31297Methanesulfonyl chlorideHCID 115875353-Bromo-1-(3-chloropyridin-2-yl)-1H-pyrazole-5-carboxylic acidHCID 251572822-Amino-5-cyano-N,3-dimethylbenzamide2×

Product 1

HCID 11578610Cyantraniliprole

Reagents, catalysts & solvents 2

HCID 962WaterSolventHCID 6342AcetonitrileSolvent

Conditions

Temperature
-10 °C

Procedure

To a mixture of 3-bromo-1-(3-chloro-2-pyridinyl)-1H-pyrazole-5-carboxylic acid (see PCT Patent Publication WO 03/015519 for preparation) (95.4% purity, 15.85 g, 50.0 mmol) and 2-amino-5-cyano-N,3-dimethylbenzamide (i.e. the product of Example 6) (9.93 g, 52.5 mmol) in acetonitrile (120 mL) was added 3-picoline (17.5 mL, 16.7 g, 180 mmol). The mixture was cooled to −10° C., and then a solution of methanesulfonyl chloride (5.4 mL, 8.0 g, 70 mmol) was added dropwise at −10 to −5° C. The mixture was stirred for 5 minutes at this temperature, and then for 3 h at 0 to 5° C. Then water (55 mL) was added dropwise. The mixture was stirred for 15 minutes, then concentrated hydrochloric acid (5.0 mL, 60 mmol) was added dropwise and the mixture was stirred at 0 to 5° C. for 1 h. Then the mixture was filtered, and the solids were washed with 2:1 acetonitrile-water (2×10 mL), and then with acetonitrile (2×10 mL), and dried under nitrogen to afford the title compound as an off-white powder, 24.70 g (99.5% uncorrected yield), m.p. 177-181° C. (decomposition).

Workup

  1. waitfor 3 h at 0 to 5° C
  2. stirringThe mixture was stirred for 15 minutes
  3. stirringthe mixture was stirred at 0 to 5° C. for 1 h
  4. filtrationThen the mixture was filtered
  5. washthe solids were washed with 2:1 acetonitrile-water (2×10 mL)
  6. dry with materialwith acetonitrile (2×10 mL), and dried under nitrogen
  7. customto afford

Sources & evidence

ORD record
ord-c0a28b0e858143d1b650d6df1f73e2ff
Source dataset
uspto-grants-2009_05
Patent number
US07528260B2

Reaction notes

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