Water → 6-cyano-2,2-dimethyl-4-(1,2-dihydro-2-oxo-4-t-butyldimethylsilyloxymethyl-1-pyridinyl)-2H-benzo[b]pyran

HRID 487629Notes

Reaction equation

HRID 487629 reaction equation
O[C@@H:2]1[C:7]([CH3:9])([CH3:8])[O:6][C:5]2[CH:10]=[CH:11][C:12]([C:14]#[N:15])=[CH:13][C:4]=2[C@H:3]1[N:16]1[CH:21]=[CH:20][C:19]([CH2:22][O:23][Si:24]([C:27]([CH3:30])([CH3:29])[CH3:28])([CH3:26])[CH3:25])=[CH:18][C:17]1=[O:31].[H-].[Na+].O>O1CCCC1>[C:14]([C:12]1[CH:11]=[CH:10][C:5]2[O:6][C:7]([CH3:9])([CH3:8])[CH:2]=[C:3]([N:16]3[CH:21]=[CH:20][C:19]([CH2:22][O:23][Si:24]([C:27]([CH3:28])([CH3:30])[CH3:29])([CH3:25])[CH3:26])=[CH:18][C:17]3=[O:31])[C:4]=2[CH:13]=1)#[N:15]

Participants

5

Reactant 3

HCID 962WaterHCID 24758Sodium hydrideHCID 131718356trans-3-hydroxy-6-cyano-3,4-dihydro-2,2-dimethyl-4-(1,2-dihydro-2-oxo-4-t-butyldimethylsilyloxymethyl-1-pyridinyl)-2H-benzo[b]pyran

Product 1

HCID 217469076-cyano-2,2-dimethyl-4-(1,2-dihydro-2-oxo-4-t-butyldimethylsilyloxymethyl-1-pyridinyl)-2H-benzo[b]pyranYield 82.1%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent

Procedure

In 50 ml of anhydrous tetrahydrofuran, is dissolved 1.32 g of trans-3-hydroxy-6-cyano-3,4-dihydro-2,2-dimethyl-4-(1,2-dihydro-2-oxo-4-t-butyldimethylsilyloxymethyl-1-pyridinyl)-2H-benzo[b]pyran obtained is Example 1. Then, 0.12 g of 60% oily sodium hydride is added to the solution at room temperature and reacted under reflux for 4 hours. After stopping the reaction by adding water, the reaction mixture is extracted with ether. The organic layer is successively washed with water and saturated aqueous solution of sodium chloride and dried over anhydrous sodium sulfate. Then, the inorganic matter is filtered off and the filtrate is concentrated under reduced pressure. The residue is purified by silica gel column chromatography using 1/7 mixture of ethyl acetate/methylene chloride as a developing solvent. Thus, 1.04 g of 6-cyano-2,2-dimethyl-4-(1,2-dihydro-2-oxo-4-t-butyldimethylsilyloxymethyl-1-pyridinyl)-2H-benzo[b]pyran is obtained.

Workup

  1. customobtained
  2. customreacted
  3. temperatureunder reflux for 4 hours
  4. customthe reaction
  5. extractionthe reaction mixture is extracted with ether
  6. washThe organic layer is successively washed with water and saturated aqueous solution of sodium chloride
  7. dry with materialdried over anhydrous sodium sulfate
  8. filtrationThen, the inorganic matter is filtered off
  9. concentrationthe filtrate is concentrated under reduced pressure
  10. customThe residue is purified by silica gel column chromatography
  11. addition1/7 mixture of ethyl acetate/methylene chloride as a developing solvent

Sources & evidence

ORD record
ord-86e3552b2ace49139127ce3b2c9bc07f
Source dataset
uspto-grants-1994_03
Patent number
US05296492

Reaction notes

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