Dimethylformamide → 5-Oxo-5,6,7,8-tetrahydronaphthalene-2-carbonitrile

HRID 1436455Notes

Reaction equation

HRID 1436455 reaction equation
FC(F)(F)S(O[C:7]1[CH:16]=[CH:15][C:14]2[C:13](=[O:17])[CH2:12][CH2:11][CH2:10][C:9]=2[CH:8]=1)(=O)=O.[CH3:20][N:21](C)C=O>[C-]#N.[Zn+2].[C-]#N.C1C=CC([P]([Pd]([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)[P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)=CC=1>[O:17]=[C:13]1[CH2:12][CH2:11][CH2:10][C:9]2[CH:8]=[C:7]([C:20]#[N:21])[CH:16]=[CH:15][C:14]1=2

Participants

5

Reactant 2

HCID 6228DimethylformamideHCID 110983845-Oxo-5,6,7,8-tetrahydronaphthalen-2-yl trifluoromethanesulfonate

Product 1

HCID 108991325-Oxo-5,6,7,8-tetrahydronaphthalene-2-carbonitrileYield 41%

Reagents, catalysts & solvents 2

HCID 11186Zinc cyanide (Zn(CN)2)CatalystHCID 178418397HCID 178418397, compoundCatalyst

Conditions

Temperature
135 °C

Procedure

A mixture of 5-oxo-5,6,7,8-tetrahydronaphthalen-2-yl trifluoromethanesulfonate (11.5 g, 39.0 mmol), prepared in the previous step, and zinc cyanide (2.7 g, 23.5 mmol) in dry dimethylformamide (100 mL) was degassed and put under a nitrogen atmosphere. Tetrakis(triphenylphosphine)palladium(0) (1.7 g, 1.5 mmol) was added and the mixture again degassed and put under a nitrogen atmosphere. The mixture was stirred at 135° C. overnight. An additional 171 mg of tetrakis(triphenylphosphine)palladium(0) was added and the reaction stirred for another 4 h. The reaction mixture was filtered through the Celite™ reagent and rinsed with ethyl acetate. The filtrate was washed with water. The layers were separated and the organic layer was dried over anhydrous sodium sulfate. The organic layer was filtered and concentrated in vacuo to give 8.1 g of crude product. Purification of the crude product on silica gel using a step-wise gradient of 5% to 15% ethyl acetate:hexane as the eluent gave 5-oxo-5,6,7,8-tetrahydro-naphthalene-2-carbonitrile (2.8 g, 41%), MS (ES) m/z 172 [M+H]+.

Workup

  1. customwas degassed
  2. customthe mixture again degassed
  3. additionAn additional 171 mg of tetrakis(triphenylphosphine)palladium(0) was added
  4. stirringthe reaction stirred for another 4 h
  5. filtrationThe reaction mixture was filtered through the Celite™ reagent
  6. washrinsed with ethyl acetate
  7. washThe filtrate was washed with water
  8. customThe layers were separated
  9. dry with materialthe organic layer was dried over anhydrous sodium sulfate
  10. filtrationThe organic layer was filtered
  11. concentrationconcentrated in vacuo
  12. customto give 8.1 g of crude product
  13. customPurification of the crude product on silica gel using a step-wise gradient of 5% to 15% ethyl acetate

Sources & evidence

ORD record
ord-f9f4a7a166d54b60a028428571cf4f3f
Source dataset
uspto-grants-2009_11
Patent number
US07618990B2

Reaction notes

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