Hydrogen Peroxide → (1S)-1-(2-Hydroxyethyl)-3,4-dihydro-1H-2-benzopyran-6-carboxamide

HRID 2056723Notes

Reaction equation

HRID 2056723 reaction equation
[OH:1][CH2:2][CH2:3][C@H:4]1[C:9]2[CH:10]=[CH:11][C:12]([C:14]#[N:15])=[CH:13][C:8]=2[CH2:7][CH2:6][O:5]1.C(=O)([O-])[O-:17].[K+].[K+].OO.C(OCC)(=O)C>CO.CS(C)=O.O>[OH:1][CH2:2][CH2:3][C@H:4]1[C:9]2[CH:10]=[CH:11][C:12]([C:14]([NH2:15])=[O:17])=[CH:13][C:8]=2[CH2:7][CH2:6][O:5]1

Participants

8

Reactant 4

HCID 784Hydrogen PeroxideHCID 8857Ethyl AcetateHCID 11430Potassium CarbonateHCID 69306499(1S)-1-(2-Hydroxyethyl)-3,4-dihydro-1H-2-benzopyran-6-carbonitrile

Product 1

HCID 69308374(1S)-1-(2-Hydroxyethyl)-3,4-dihydro-1H-2-benzopyran-6-carboxamide

Reagents, catalysts & solvents 3

HCID 679Dimethyl SulfoxideSolventHCID 887MethanolSolventHCID 962WaterSolvent

Procedure

To a solution of crude (1S)-1-(2-hydroxyethyl)-3,4-dihydro-1H-2-benzopyran-6-carbonitrile (178 g, 0.88 mol) in methanol (460 mL) and DMSO (125 mL) was added potassium carbonate (13 g, 94 mmol). 35% hydrogen peroxide (102 mL) was then added dropwise while maintaining the temperature of the mixture below 50° C. The reaction mixture was then allowed to stir for 1 h at ambient temperature. Analysis of an aliquot by silica TLC (ethyl acetate) indicated that the reaction was complete. Water (130 mL) was added and methanol removed in vacuo. Water (800 mL) and 1N HCl (100 mL) were added and the mixture allowed to stir overnight. The solid was filtered, washed with water, and dried. Recrystallization from methyl(i-butyl)ketone gave the title compound.

Workup

  1. temperaturewhile maintaining the temperature of the mixture below 50° C
  2. custommethanol removed in vacuo
  3. additionWater (800 mL) and 1N HCl (100 mL) were added
  4. stirringto stir overnight
  5. filtrationThe solid was filtered
  6. washwashed with water
  7. customdried
  8. customRecrystallization from methyl(i-butyl)ketone

Sources & evidence

ORD record
ord-3a6f00b36b2c48459a05aa89c3c2a8e1
Source dataset
uspto-grants-2008_02
Patent number
US07335660B2

Reaction notes

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