Nitrogen → 10-Formylanthracene-9-carbonitrile

HRID 1960174Notes

Reaction equation

HRID 1960174 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 31374DimethylacetamideSolvent3×

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 bottom flask with three way stopcock with vacuum line in one side and ultra dry N2 balloon on the other side. Evacuation of the flask was done and DMAC was kept under N2 environment. To 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 was allowed to enter the flask via 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, organic layer was again washed with saturated solution of NH4Cl. The EtOAc layer was dried over anhydrous Na2SO4, filtered and removed in vacuo to give yellow solid 7 in 89% yield by NMR.

Workup

  1. customAs reaction
  2. customflask was evacuated
  3. additionDMAC (4 mL) was added to the flask via a syringe
  4. customThe whole assembly was transferred in an oil bath at 80° C.
  5. customthe consumption of 6 by TLC (40% CH2Cl2/Hexane), EtOAc (20 mL)
  6. additionwas added to the reaction mixture
  7. customcrude reaction mixture
  8. washwas washed with saturated solution of K2CO3, organic layer
  9. washwas again washed with saturated solution of NH4Cl
  10. dry with materialThe EtOAc layer was dried over anhydrous Na2SO4
  11. filtrationfiltered
  12. customremoved in vacuo

Sources & evidence

ORD record
ord-ebb68b4101fd4cf2b50106370e5cde30
Source dataset
uspto-grants-2013_04
Patent number
US08410311B1

Reaction notes

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