N,N,N',N'-Tetramethylethylenediamine → 7-Oxo-5,6,7,8-tetrahydronaphthalene-2-carbonitrile

HRID 2173240Notes

Reaction equation

HRID 2173240 reaction equation
Br[C:2]1[CH:11]=[C:10]2[C:5]([CH2:6][CH2:7][C:8](=[O:12])[CH2:9]2)=[CH:4][CH:3]=1.[CH3:13][N:14](CCN(C)C)C>CN(C=O)C.[C-]#N.[C-]#N.[Zn+2].C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.[Pd].[Pd].CC1(C)C2C(=C(P(C3C=CC=CC=3)C3C=CC=CC=3)C=CC=2)OC2C(P(C3C=CC=CC=3)C3C=CC=CC=3)=CC=CC1=2>[O:12]=[C:8]1[CH2:9][C:10]2[CH:11]=[C:2]([C:13]#[N:14])[CH:3]=[CH:4][C:5]=2[CH2:6][CH2:7]1

Participants

7

Reactant 2

HCID 8037N,N,N',N'-TetramethylethylenediamineHCID 36915747-Bromo-2-tetralone

Product 1

HCID 675155667-Oxo-5,6,7,8-tetrahydronaphthalene-2-carbonitrileYield 186.4%

Reagents, catalysts & solvents 4

HCID 11186Zinc cyanide (Zn(CN)2)CatalystHCID 6360441,1'-(9,9-Dimethyl-9H-xanthene-4,5-diyl)bis(1,1-diphenylphosphine)CatalystHCID 9811564Bis(dibenzylideneacetone)palladiumCatalystHCID 6228DimethylformamideSolvent

Conditions

Temperature
160 °C

Procedure

A solution of 7-bromo-3,4-dihydronaphthalen-2(1H)-one (500 mg, 2.2 mmol) in 5 mL of anhydrous DMF in a 10 mL CEM microwave tube was added Zn(CN)2 (515 mg, 4.4 mmol), Pd2(dba)3 (55 mg, 0.034 mmol), TMEDA (55 mg, 0.47 mmol) and Xantphos (29 mg, 0.05 mmol) sucessively. The reaction tube was sealed and heated to 160° C. under microwave irradiation with a 5 min hold time and 300 W maxium power input. After cooling under a stream of compressed air, the reaction mixture was washed with EtOAc through a Celite® with a thin layer of silica gel in the middle size. The filtrate was washed with saturated bine, dried over anhydrous sodium sulfate and concentrated. The residue was purified by preparative TLC to afford 7-oxo-5,6,7,8-tetrahydronaphthalene-2-carbonitrile (150 mg, yield 40%).

Workup

  1. customThe reaction tube was sealed
  2. temperatureAfter cooling under a stream of compressed air
  3. washthe reaction mixture was washed with EtOAc through a Celite® with a thin layer of silica gel in the middle size
  4. washThe filtrate was washed with saturated bine
  5. dry with materialdried over anhydrous sodium sulfate
  6. concentrationconcentrated
  7. customThe residue was purified by preparative TLC

Sources & evidence

ORD record
ord-a1cbe02df2e74fcdb93dd3442519135f
Source dataset
uspto-grants-2015_06
Patent number
US09056859B2

Reaction notes

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