Hydrogen Peroxide → HCID 9862505, compound

HRID 2299566Notes

Reaction equation

HRID 2299566 reaction equation
[C:1]1([S:7]([O:10][C:11]2[CH:21]=[CH:20][C:14]3[S:15][CH:16]=[C:17]([CH2:18][OH:19])[C:13]=3[CH:12]=2)(=[O:9])=[O:8])[CH:6]=[CH:5][CH:4]=[CH:3][CH:2]=1.C1(S(OC2C=CC(SCC#C)=CC=2)(=O)=[O:29])C=CC=CC=1.Cl[O-].[Na+].S(=O)(=O)(O)O.S([O-])([O-])=O.[Na+].[Na+].Cl([O-])=O.[Na+].OO>C(#N)C.O.CC1(C)N([O])C(C)(C)CCC1>[C:1]1([S:7]([O:10][C:11]2[CH:21]=[CH:20][C:14]3[S:15][CH:16]=[C:17]([C:18]([OH:29])=[O:19])[C:13]=3[CH:12]=2)(=[O:8])=[O:9])[CH:6]=[CH:5][CH:4]=[CH:3][CH:2]=1

Participants

11

Reactant 7

HCID 784Hydrogen PeroxideHCID 1118Sulfuric AcidHCID 24437Sodium SulfiteHCID 10892558HCID 10892558, compoundHCID 10924734HCID 10924734, compoundHCID 23665760Sodium Hypochlorite2×HCID 23668197Sodium Chlorite

Product 1

HCID 9862505HCID 9862505, compoundYield 51.7%

Reagents, catalysts & solvents 3

HCID 2724126TempoCatalystHCID 962WaterSolventHCID 6342AcetonitrileSolvent2×

Procedure

The compound (4) (51.26 g, 155 mmol) prepared in above (3) was dissolved in acetonitrile (1.54 L), and TEMPO (2,2,6,6-tetramethylpiperidine-1-oxyl, 250 mg, 0.01 eq.) was added thereto. To the mixture was added dropwise 0.81 N aqueous sodium hypochlorite, which had been prepared by diluting 1.63 N aqueous sodium hypochlorite (150 ml) with water (75 ml), adjusting pH 8.6 with 1 N sulfuric acid, and adjusting the total volume to 300 ml, over 15 minutes, while maintaining the inner temperature between −1° C. and 8° C. After stirring for 25 minutes at this temperature, 1 N aqueous sodium sulfite (32 ml) was added. Subsequently, 79% sodium chlorite (27.48 g, 240 mmol) and 31% aqueous hydrogen peroxide (23.26 g, 212 mmol) were added under ice-cooling. The cooling bath was removed and the mixture was stirred for 2 hours. The reaction was diluted with water (1.5 L), adjusted to pH 3 with 1 N hydrochloric acid and the deposited crystals were filtered, and washed twice with water (200 ml), acetonitrile (50 ml) to provide 32.4 g of crude crystals. The crude crystals (32.4 g) were suspended in acetonitrile (224 ml), refluxed for 15 minutes and cooled on ice. The crystals were filtered and washed with acetonitrile (65 ml) to provide 26.79 g of the title compound (6). Yield: 51.7%, mp 202-203° C.

Workup

  1. customhad been prepared
  2. temperaturewhile maintaining the inner temperature between −1° C. and 8° C
  3. additionwas added
  4. temperaturecooling
  5. customThe cooling bath was removed
  6. additionThe reaction was diluted with water (1.5 L)
  7. filtrationthe deposited crystals were filtered
  8. washwashed twice with water (200 ml), acetonitrile (50 ml)
  9. customto provide 32.4 g of crude crystals
  10. temperaturerefluxed for 15 minutes
  11. temperaturecooled on ice
  12. filtrationThe crystals were filtered
  13. washwashed with acetonitrile (65 ml)

Sources & evidence

ORD record
ord-b81527dd63e34c769f644b23936f8849
Source dataset
uspto-grants-2002_12
Patent number
US06495702B2

Reaction notes

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