Hydrogen Peroxide → HCID 11635134, compound

HRID 736843Notes

Reaction equation

HRID 736843 reaction equation
[Cl:1][C:2]1[CH:7]=[CH:6][C:5]([CH2:8]/[C:9](/[C:29]2[CH:34]=[CH:33][CH:32]=[C:31]([C:35]#[N:36])[CH:30]=2)=[C:10](/[NH:12][C:13](=[O:28])[C:14]([CH3:27])([O:16][C:17]2[CH:22]=[CH:21][C:20]([C:23]([F:26])([F:25])[F:24])=[CH:19][N:18]=2)[CH3:15])\[CH3:11])=[CH:4][CH:3]=1.C([O-])([O-])=[O:38].[K+].[K+].OO.CCCCCCC>C(OC(C)C)(=O)C.CS(C)=O>[Cl:1][C:2]1[CH:7]=[CH:6][C:5]([CH2:8]/[C:9](/[C:29]2[CH:30]=[C:31]([CH:32]=[CH:33][CH:34]=2)[C:35]([NH2:36])=[O:38])=[C:10](/[NH:12][C:13](=[O:28])[C:14]([CH3:15])([O:16][C:17]2[CH:22]=[CH:21][C:20]([C:23]([F:25])([F:26])[F:24])=[CH:19][N:18]=2)[CH3:27])\[CH3:11])=[CH:4][CH:3]=1

Participants

7

Reactant 4

HCID 784Hydrogen PeroxideHCID 8900HeptaneHCID 11430Potassium CarbonateHCID 11548032HCID 11548032, compound2×

Product 1

HCID 11635134HCID 11635134, compoundYield 0.02%

Reagents, catalysts & solvents 2

HCID 679Dimethyl SulfoxideSolventHCID 7915Isopropyl AcetateSolvent

Conditions

Temperature
20 °C

Procedure

To a 5 L, 3-necked round bottom flask equipped with overhead stirrer, thermocouple, and nitrogen inlet was added 524 g of the cyano enamide product of Example 14, N-[(1Z)-3-(4-chlorophenyl)-2-(3-cyanophenyl)-1-methylprop-1-en-1-yl]-2-methyl-2-{[5-(trifluoromethyl)pyridin-2-yl]oxy}propanamide, and 112 g K2CO3. DMSO (2.7 L) was charged and the vessel was submerged in a RT water bath. Hydrogen peroxide solution (165 mol of a 30% aqueous solution) was slowly added to the reactor such that the temperature never rose above 25° C. After the addition was complete, the reaction was aged for 1 hour. The batch was diluted with 1 L of isopropyl acetate and filtered over a bed of SOLKA FLOC. The bed was washed with 4.5 L of isopropyl acetate and the resulting solution was transferred to a 50 L extractor containing 5.5 L of water. The layers were separated and the organic layer was washed twice with 3.1 L of water, concentrated to 5 L, and solvent switched to 5 L toluene at −60° C. Upon completion of the solvent switch, 500 mol of heptane was added and the mixture was cooled to 20° C. The batch was aged for 30 minutes at 20° C., then filtered and washed with 1 L of toluene. The resulting solid was dried overnight under a stream of nitrogen to afford 522 g of the title compound (99.4 LCAP, 98.0 wt %, 0.02% dppb-oxide, 512 g assay).

Workup

  1. customTo a 5 L, 3-necked round bottom flask equipped with overhead stirrer
  2. customwas submerged in a RT
  3. additionAfter the addition
  4. filtrationfiltered over a bed of SOLKA FLOC
  5. washThe bed was washed with 4.5 L of isopropyl acetate
  6. additioncontaining 5.5 L of water
  7. customThe layers were separated
  8. washthe organic layer was washed twice with 3.1 L of water
  9. concentrationconcentrated to 5 L, and solvent
  10. customswitched to 5 L toluene at −60° C
  11. waitThe batch was aged for 30 minutes at 20° C.
  12. filtrationfiltered
  13. washwashed with 1 L of toluene
  14. customThe resulting solid was dried overnight under a stream of nitrogen

Sources & evidence

ORD record
ord-72395d954614436eb370c17aeafae69d
Source dataset
uspto-grants-2009_09
Patent number
US07595417B2

Reaction notes

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