Hydrochloric Acid → 10-Formylanthracene-9-carbonitrile

HRID 1381773Notes

Reaction equation

HRID 1381773 reaction equation
N#N.Cl[C:4]1[C:17]2[C:12](=[CH:13][CH:14]=[CH:15][CH:16]=2)[C:11]([CH:18]=[O:19])=[C:10]2[C:5]=1[CH:6]=[CH:7][CH:8]=[CH:9]2.[C:20]([Cu])#[N:21].Cl>C1(C)C=CC=CC=1.[Pd](Cl)Cl.C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.O.CN(C=O)C.CN1CCCC1=O>[CH:18]([C:11]1[C:12]2[C:17](=[CH:16][CH:15]=[CH:14][CH:13]=2)[C:4]([C:20]#[N:21])=[C:5]2[C:10]=1[CH:9]=[CH:8][CH:7]=[CH:6]2)=[O:19]

Participants

10

Reactant 4

HCID 313Hydrochloric AcidHCID 947NitrogenHCID 8270310-Chloro-9-anthraldehydeHCID 178418546HCID 178418546, compound

Product 1

HCID 1331933210-Formylanthracene-9-carbonitrileYield 68%

Reagents, catalysts & solvents 5

HCID 6102075Dichlorobis(triphenylphosphine)palladiumCatalystHCID 962WaterSolventHCID 1140TolueneSolventHCID 6228DimethylformamideSolventHCID 13387N-methyl-2-pyrrolidoneSolvent

Procedure

A 25 mL 2-neck RB flask fitted with thermometer, condenser, N2 inlet, bubbler and stirring bar was charged with 10-chloro-9-anthraldehyde (Aldrich, 5 g, 21 mmol, CuCN (Fisher, 2.14 g, 24 mmol), N-methylpyrrolidinone (Aldrich, 100 mL), dry DMF (Aldrich, 15 mL), and bis(triphenylphosphine) palladium dichloride (Fluka Chemical Corp., 255 Hauser Ave., Hauppauge, NY, 11787, 0.08 g, 0.1 mmol). The mixture was warmed to 170° and stirred 15 h under N2. After 1.5 h, the mixture became homogeneous. The reaction was cooled to 70° and poured into a solution composed of 16 g of FeCl3.6H2O, (Mallinckrodt), 70 mL of 1.0M HCl and 400 mL H2O. The resulting mixture was stirred at 60°-70° for 1 h, filtered and a crude orange solid isolated. This material was dissolved in hot PhCH3 (1 L) and passed through a small plug (100 g) of SiO2. The filtrate was then concentrated to 75 mL and diluted with hexane (200 mL). The orange solid which formed was collected by filtration and dried at 50° to give 3.17 g (68%) of 10-formyl-9-anthracenecarbonitrile mp 270°-275°, (C, H, N).

Workup

  1. temperatureThe mixture was warmed to 170°
  2. stirringstirred 15 h under N2
  3. temperatureThe reaction was cooled to 70°
  4. additionpoured into a solution
  5. stirringThe resulting mixture was stirred at 60°-70° for 1 h
  6. filtrationfiltered
  7. customa crude orange solid isolated
  8. concentrationThe filtrate was then concentrated to 75 mL
  9. additiondiluted with hexane (200 mL)
  10. customThe orange solid which formed
  11. filtrationwas collected by filtration
  12. customdried at 50°

Sources & evidence

ORD record
ord-e3345a54ae144afebf72d37c2d9ccd49
Source dataset
uspto-grants-1989_02
Patent number
US04803221

Reaction notes

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