Phenyl thioxochloroformate → 6-cyano-2,2-dimethyl-4-{1,2-dihydro-2-oxo-4-(1-phenoxythiocarbonyloxy-3-t-butyldimethylsilyloxypropyl)-1-pyridinyl}-2H-benzo[b]pyran

HRID 487649Notes

Reaction equation

HRID 487649 reaction equation
[C:1]([C:3]1[CH:33]=[CH:32][C:6]2[O:7][C:8]([CH3:31])([CH3:30])[CH:9]=[C:10]([N:11]3[CH:16]=[CH:15][C:14]([CH:17]([OH:28])[CH2:18][CH2:19][O:20][Si:21]([C:24]([CH3:27])([CH3:26])[CH3:25])([CH3:23])[CH3:22])=[CH:13][C:12]3=[O:29])[C:5]=2[CH:4]=1)#[N:2].[O:34]([C:41](Cl)=[S:42])[C:35]1[CH:40]=[CH:39][CH:38]=[CH:37][CH:36]=1.C(=O)([O-])O.[Na+]>C(#N)C.CN(C)C1C=CN=CC=1>[C:1]([C:3]1[CH:33]=[CH:32][C:6]2[O:7][C:8]([CH3:31])([CH3:30])[CH:9]=[C:10]([N:11]3[CH:16]=[CH:15][C:14]([CH:17]([O:28][C:41]([O:34][C:35]4[CH:40]=[CH:39][CH:38]=[CH:37][CH:36]=4)=[S:42])[CH2:18][CH2:19][O:20][Si:21]([C:24]([CH3:26])([CH3:27])[CH3:25])([CH3:23])[CH3:22])=[CH:13][C:12]3=[O:29])[C:5]=2[CH:4]=1)#[N:2]

Participants

6

Reactant 3

HCID 70498Phenyl thioxochloroformateHCID 516892Sodium BicarbonateHCID 217469036-cyano-2,2-dimethyl-4-{1,2-dihydro-2-oxo-4-(1-hydroxy-3-t-butyldimethylsilyloxypropyl)-1-pyridinyl}-2H-benzo[b]pyran

Product 1

HCID 217469246-cyano-2,2-dimethyl-4-{1,2-dihydro-2-oxo-4-(1-phenoxythiocarbonyloxy-3-t-butyldimethylsilyloxypropyl)-1-pyridinyl}-2H-benzo[b]pyran

Reagents, catalysts & solvents 2

HCID 142844-(Dimethylamino)pyridineCatalystHCID 6342AcetonitrileSolvent

Procedure

In 30 ml of anhydrous acetonitrile, is dissolved 1.46 g of 6-cyano-2,2-dimethyl-4-{2-oxo-4-(1-hydroxy-3-t-butyldimethylsilyloxypropyl)-1-pyridinyl}-2H-benzo[b]pyran obtained in Example 38. Then, 0.73 g of 4-dimethylaminopyridine and 0.79 ml of phenoxythiocarbonyl chloride are added at room temperature, and reacted at that temperature for 6 hours. After stopping the reaction by adding 0.1M aqueous solution of sodium hydrogen carbonate, the reaction mixture is extracted with ether. The organic layer is washed successively 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 1/2 mixture of ethyl acetate/n-hexane as a developing solvent. Thus, 1.20 g of 6-cyano-2,2-dimethyl-4-{1,2-dihydro-2-oxo-4-(1-phenoxythiocarbonyloxy-3-t-butyldimethylsilyloxypropyl)-1-pyridinyl}-2H-benzo[ b]pyran is obtained.

Workup

  1. customreacted at that temperature for 6 hours
  2. customthe reaction
  3. extractionthe reaction mixture is extracted with ether
  4. washThe organic layer is washed successively 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. addition1/2 mixture of ethyl acetate/n-hexane as a developing solvent

Sources & evidence

ORD record
ord-0ab9e4e04f24414cb710e8089f3caeac
Source dataset
uspto-grants-1994_03
Patent number
US05296492

Reaction notes

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