m-Chloroperbenzoic acid → HCID 53879492, compound

HRID 1740117Notes

Reaction equation

HRID 1740117 reaction equation
[CH2:1]([O:3][C:4]([C:6]1[C:7]([CH2:22][CH3:23])=[N:8][N:9]([C:13]2[C:18]([CH3:19])=[CH:17][C:16]([Br:20])=[CH:15][C:14]=2[CH3:21])[C:10]=1SC)=[O:5])[CH3:2].[C:24](=O)(O)[O-].[Na+].ClC1C=CC=C(C(OO)=O)C=1.[S:40](=[O:43])(O)[O-:41].[Na+]>C1COCC1.O>[CH2:1]([O:3][C:4]([C:6]1[C:7]([CH2:22][CH3:23])=[N:8][N:9]([C:13]2[C:18]([CH3:19])=[CH:17][C:16]([Br:20])=[CH:15][C:14]=2[CH3:21])[C:10]=1[S:40]([CH3:24])(=[O:43])=[O:41])=[O:5])[CH3:2]

Participants

7

Reactant 4

HCID 70297m-Chloroperbenzoic acidHCID 516892Sodium BicarbonateHCID 23665763Sodium BisulfiteHCID 54502946HCID 54502946, compound

Product 1

HCID 53879492HCID 53879492, compound

Reagents, catalysts & solvents 2

HCID 962WaterSolventHCID 8028TetrahydrofuranSolvent2×

Conditions

Temperature
170 °C

Procedure

A solution of 2.6 g (6.56 mmol) of 1-(4-bromo-2,6-dimethylphenyl)-3-ethyl-5-methylthio-1H-pyrazole4-carboxylic acid ethyl ester in 50 mL of THF in a 125 mL 3-neck RBF was stirred under N2 and cooled to 170° C. Then 0.826 9 (9.80 mmol) of anhydrous sodium bicarbonate was added followed by a solution of 6.79 g (19.6 mmol) of m-chloroperbenzoic acid dissolved in 40 mL of THF. During the addition, the temperature of the reaction mixture was not allowed to rise above 20° C. After 1 hour, an aliquot workup showed that the reaction mixture consisted of about 34% of the desired sulfone and about 66% of the intermediate sulfoxide and after stirring overnight at room temperature, the conversion to sulfone was complete. A solution of 50 mL of 20% sodium bisulfite was then added and the resulting reaction mixture was stirred for 15 minutes. The reaction mixture was diluted with 50 mL of water and the product was extracted into 100 mL of CH2Cl2. The organic extracts were washed twice with saturated bicarbonate solution and once with 20% sodium bisulfite solution. The organic layer was dried over sodium sulfate and evaporated to give the desired product (2.91 g) as a gum. 1H-NMR (CDCl3) δ 0.28 (3H,t,J=7), 1.42 (3H, t, J=7), 1.97 (6H, s), 2.93 (2H, q, J=7), 3.39 (3H, s), 4.42 (2H, q, J=7), 7.29 (2H, s).

Workup

  1. additionDuring the addition
  2. customto rise above 20° C
  3. customthe resulting reaction mixture
  4. stirringwas stirred for 15 minutes
  5. extractionthe product was extracted into 100 mL of CH2Cl2
  6. washThe organic extracts were washed twice with saturated bicarbonate solution and once with 20% sodium bisulfite solution
  7. dry with materialThe organic layer was dried over sodium sulfate
  8. customevaporated

Sources & evidence

ORD record
ord-d66304d71e3f42d1a3d0e0978c84bee9
Source dataset
uspto-grants-1999_10
Patent number
US05968944

Reaction notes

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