Nitrogen → 10-Formylanthracene-9-carbonitrile

HRID 926435Notes

Reaction equation

HRID 926435 reaction equation
O=O.[N:3]#N.BrC1[C:7]2[C:12]([C:13]([CH:20]=[O:21])=[C:14]3C=1[CH:18]=[CH:17][CH:16]=[CH:15]3)=C[CH:10]=[CH:9][CH:8]=2.[C:22](P)([CH3:25])([CH3:24])[CH3:23]>CN(C)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].[Zn]>[C:23]([C:22]1[C:25]2[C:12]([C:13]([CH:20]=[O:21])=[C:14]3[C:24]=1[CH:18]=[CH:17][CH:16]=[CH:15]3)=[CH:7][CH:8]=[CH:9][CH:10]=2)#[N:3]

Participants

9

Reactant 4

HCID 947NitrogenHCID 977OxygenHCID 123165tert-ButylphosphineHCID 60074310-Bromoanthracene-9-carbaldehyde

Product 1

HCID 1331933210-Formylanthracene-9-carbonitrileYield 89%

Reagents, catalysts & solvents 4

HCID 11186Zinc cyanide (Zn(CN)2)CatalystHCID 23994ZincCatalystHCID 9811564Bis(dibenzylideneacetone)palladiumCatalystHCID 31374DimethylacetamideSolvent2×

Conditions

Temperature
80 °C

Procedure

DMAC (N,N-dimethylacetamide) was used as a solvent. As reaction is oxygen sensitive, DMAC was placed in three-necked round-bottomed flask equipped with a three-way stopcock with a vacuum line attached on one side and an ultra-dry N2 filled balloon on the other side. With this setup, the flask headspace could be readily evacuated and nitrogen gas admitted to the evacuated space. Thus, DMAC was kept under a N2 environment. To the three-necked flask Bromoaldehyde 6 (25 mg, 0.088 mmol), Zn(CN)2 (18.5 mg, 0.157 mmol), Pd2(dba)3 (2.09 mg, 0.002 mmol), Zn dust (1 mg, 0.022 mmol) were weighed out and flask was evacuated and N2 gas was allowed to enter the flask via adjustment of the three way stopcock. DMAC (4 mL) was added to the flask via a syringe keeping the flask under vacuum. t-Butyl phosphine (1.77 mg, 0.009 mmol) was added via syringe. The whole assembly was transferred in an oil bath at 80° C. and let the reaction stir at 80° C. for three hours. After monitoring the consumption of 6 by TLC (40% CH2Cl2/Hexane), EtOAc (20 mL) was added to the reaction mixture and crude reaction mixture was washed with saturated solution of K2CO3, and the organic layer was separated and washed with saturated solution of NH4Cl. The EtOAc layer was dried over anhydrous Na2SO4, filtered and concentrated in vacuo to give yellow solid 7 in 89% yield by NMR.

Workup

  1. customAs reaction
  2. customwas placed in three-necked round-bottomed flask
  3. customequipped with a three-way stopcock with a vacuum line
  4. customWith this setup, the flask headspace could be readily evacuated
  5. customflask was evacuated
  6. additionDMAC (4 mL) was added to the flask via a syringe
  7. customThe whole assembly was transferred in an oil bath at 80° C.
  8. customthe consumption of 6 by TLC (40% CH2Cl2/Hexane), EtOAc (20 mL)
  9. additionwas added to the reaction mixture
  10. customcrude reaction mixture
  11. washwas washed with saturated solution of K2CO3
  12. customthe organic layer was separated
  13. washwashed with saturated solution of NH4Cl
  14. dry with materialThe EtOAc layer was dried over anhydrous Na2SO4
  15. filtrationfiltered
  16. concentrationconcentrated in vacuo

Sources & evidence

ORD record
ord-b887da57ccd341d18246dc9656273489
Source dataset
uspto-grants-2016_03
Patent number
US09285320B2

Reaction notes

Loading…