Trimethylsilyl cyanide → HCID 20069061, compound

HRID 982099Notes

Reaction equation

HRID 982099 reaction equation
[OH:1][C:2]1[C:11]([O:12][CH3:13])=[CH:10][CH:9]=[C:8]2[C:3]=1[CH2:4][CH:5]([C:15]1[CH:20]=[CH:19][CH:18]=[CH:17][CH:16]=1)[CH2:6][C:7]2=[O:14].C[Si]([C:25]#[N:26])(C)C.[H-].[Al+3].[Li+].[H-].[H-].[H-]>C(#N)C.C1COCC1.[I-].[Zn+2].[I-]>[NH2:26][CH2:25][C:7]1([OH:14])[C:8]2[C:3](=[C:2]([OH:1])[C:11]([O:12][CH3:13])=[CH:10][CH:9]=2)[CH2:4][CH:5]([C:15]2[CH:20]=[CH:19][CH:18]=[CH:17][CH:16]=2)[CH2:6]1

Participants

7

Reactant 3

HCID 82115Trimethylsilyl cyanideHCID 20069042HCID 20069042, compoundHCID 21226445Aluminium lithium hydride

Product 1

HCID 20069061HCID 20069061, compoundYield 75.6%

Reagents, catalysts & solvents 3

HCID 9883512zinc(II)iodideCatalystHCID 6342AcetonitrileSolventHCID 8028TetrahydrofuranSolvent2×

Procedure

To a suspension of 5-hydroxy-6-methoxy-3-phenyl-1,2,3,4-tetrahydro-1-naphthalenone (1.13 g, 4.2 mmol), from Step 2, in 8 mL of anhydrous acetonitrile, was added 2.4 mL (18 mmol) of trimethylsilylcyanide and a catalytic amount of zinc iodide. The reaction mixture was heated at reflux for 4 h and then cooled and concentrated. The residue was kept overnight at 0° C. under nitrogen atmosphere and then dissolved in 16 mL of anhydrous THF. The THF solution was added dropwise to a suspension of 0.77 g (20 mmol) of lithium aluminum hydride (LAH) in 8 mL of THF at 0° C. under a nitrogen atmosphere. The mixture was allowed to warm to ambient temperature and then was heated at reflux for 1 h, allowed to cool to ambient temperature and was stirred at ambient temperature for 2 h. The reaction was quenched by the sequential addition of 0.8 mL of water, 0.8 mL of 15% aqueous sodium hydroxide solution and 2.8 mL of water. Anhydrous magnesium sulfate was added to the mixture and the suspension was diluted with 50 mL of methylene chloride and filtered. The filter cake was washed with 200 mL of methylene chloride and 300 mL of ethyl acetate and discarded. The combined filtrates were evaporated to give 0.95 g (75.4% yield) of the title compound. This product was taken on to the next step without purification.

Workup

  1. temperatureThe reaction mixture was heated
  2. temperatureat reflux for 4 h
  3. temperaturecooled
  4. concentrationconcentrated
  5. dissolutiondissolved in 16 mL of anhydrous THF
  6. temperaturewas heated
  7. temperatureat reflux for 1 h
  8. temperatureto cool to ambient temperature
  9. customThe reaction was quenched by the sequential addition of 0.8 mL of water, 0.8 mL of 15% aqueous sodium hydroxide solution and 2.8 mL of water
  10. additionAnhydrous magnesium sulfate was added to the mixture
  11. additionthe suspension was diluted with 50 mL of methylene chloride
  12. filtrationfiltered
  13. washThe filter cake was washed with 200 mL of methylene chloride and 300 mL of ethyl acetate
  14. customThe combined filtrates were evaporated

Sources & evidence

ORD record
ord-bc7e66ee64d34a3182a799aea7b2a9da
Source dataset
uspto-grants-1991_02
Patent number
US04994486

Reaction notes

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