Water → trans-3-acetoxy-6-cyano-3,4-dihydro-2,2-dimethyl-4-(1,2-dihydro-2-oxo-4-t-butyldimethylsilyloxymethyl-1-pyridinyl)-2H-benzo[b]pyran

HRID 487627Notes

Reaction equation

HRID 487627 reaction equation
[OH:1][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].N1C=CC=CC=1.[C:38](OC(=O)C)(=[O:40])[CH3:39].O>C(Cl)Cl.CN(C)C1C=CN=CC=1>[C:38]([O:1][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])(=[O:40])[CH3:39]

Participants

7

Reactant 4

HCID 962WaterHCID 1049PyridineHCID 7918Acetic AnhydrideHCID 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 131718355trans-3-acetoxy-6-cyano-3,4-dihydro-2,2-dimethyl-4-(1,2-dihydro-2-oxo-4-t-butyldimethylsilyloxymethyl-1-pyridinyl)-2H-benzo[b]pyran

Reagents, catalysts & solvents 2

HCID 142844-(Dimethylamino)pyridineCatalystHCID 6344DichloromethaneSolvent

Procedure

In 15 ml of anhydrous methylene chloride, 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 in Example 1. Then, 0.49 ml of pyridine and 73 mg of 4-dimethylaminopyridine are added. Then, 0.43 ml of acetic anhydride is dropped thereinto at 0° C. and reacted at room temperature for 30 minutes. After stopping the reaction by adding water to the reaction mixture, it 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. The inorganic matter is filtered off and the filtrate is concentrated under reduced pressure. The residue is purified by silica gel column chromatography using 1/3 mixture of ethyl acetate/methylene chloride as a developing solvent to obtain 1.45 g of trans-3-acetoxy-6-cyano-3,4-dihydro-2,2-dimethyl-4-(1,2-dihydro-2-oxo-4-t-butyldimethylsilyloxymethyl-1-pyridinyl)-2H-benzo[b]pyran.

Workup

  1. customat 0° C. and reacted at room temperature for 30 minutes
  2. customthe reaction
  3. extractionis extracted with ether
  4. washThe organic layer is successively washed with water and saturated aqueous solution of sodium chloride
  5. dry with materialdried over anhydrous sodium sulfate
  6. filtrationThe inorganic matter is filtered off
  7. concentrationthe filtrate is concentrated under reduced pressure
  8. customThe residue is purified by silica gel column chromatography
  9. addition1/3 mixture of ethyl acetate/methylene chloride as a developing solvent

Sources & evidence

ORD record
ord-7231cbefef484ca2adcde9aa423ac46a
Source dataset
uspto-grants-1994_03
Patent number
US05296492

Reaction notes

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