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

HRID 487650Notes

Reaction equation

HRID 487650 reaction equation
[C:1]([C:3]1[CH:42]=[CH:41][C:6]2[O:7][C:8]([CH3:40])([CH3:39])[CH:9]=[C:10]([N:11]3[CH:16]=[CH:15][C:14]([CH:17](OC(OC4C=CC=CC=4)=S)[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:38])[C:5]=2[CH:4]=1)#[N:2].N(C(C)(C)C#N)=NC(C)(C)C#N.C([SnH](CCCC)CCCC)CCC>C1(C)C=CC=CC=1>[C:1]([C:3]1[CH:42]=[CH:41][C:6]2[O:7][C:8]([CH3:40])([CH3:39])[CH:9]=[C:10]([N:11]3[CH:16]=[CH:15][C:14]([CH2:17][CH2:18][CH2:19][O:20][Si:21]([C:24]([CH3:25])([CH3:26])[CH3:27])([CH3:23])[CH3:22])=[CH:13][C:12]3=[O:38])[C:5]=2[CH:4]=1)#[N:2]

Participants

5

Reactant 3

HCID 5948TributylstannaneHCID 6547AzobisisobutyronitrileHCID 217469246-cyano-2,2-dimethyl-4-{1,2-dihydro-2-oxo-4-(1-phenoxythiocarbonyloxy-3-t-butyldimethylsilyloxypropyl)-1-pyridinyl}-2H-benzo[b]pyran

Product 1

HCID 217469126-cyano-2,2-dimethyl-4-{1,2-dihydro-2-oxo-4-(3-t-butyldimethylsilyloxypropyl)-1-pyridinyl}-2H-benzo[b]pyranYield 92.5%

Reagents, catalysts & solvents 1

HCID 1140TolueneSolvent

Procedure

In 40 ml of anhydrous toluene, is dissolved 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 obtained in Example 39. Then, 0.66 g of 2,2'-azobisisobutyronitrile and 1.16 g of tri-n-butyltin hydride are added at room temperature and reacted at 100° C. for 30 minutes. After the reaction, the reaction mixture is directly purified by silica gel column chromatography using 1/1 mixture of ethyl acetate/n-hexane as a developing solvent. Thus, 0.83 g of 6-cyano-2,2-dimethyl-4-{1,2-dihydro-2-oxo-4-(3-t-butyldimethylsilyloxypropyl)-1-pyridinyl}-2H-benzo[b]pyran is obtained.

Workup

  1. customreacted at 100° C. for 30 minutes
  2. customAfter the reaction
  3. customthe reaction mixture is directly purified by silica gel column chromatography
  4. addition1/1 mixture of ethyl acetate/n-hexane as a developing solvent

Sources & evidence

ORD record
ord-289c2fe07e704914bf8f7fe6965b8b01
Source dataset
uspto-grants-1994_03
Patent number
US05296492

Reaction notes

Loading…