Phosphate → 2-Formyl-6-nitrobenzonitrile

HRID 471675

Reaction equation

HRID 471675 reaction equation
COC([O:7][CH3:8])N(C)C.C[C:10]1[CH:17]=[CH:16][CH:15]=[C:14]([N+:18]([O-:20])=[O:19])[C:11]=1[C:12]#[N:13].P([O-])([O-])([O-])=O>CN(C=O)C.C1COCC1>[CH:8]([C:10]1[CH:17]=[CH:16][CH:15]=[C:14]([N+:18]([O-:20])=[O:19])[C:11]=1[C:12]#[N:13])=[O:7]

Participants

6

Reactant 3

HCID 1061PhosphateHCID 746696-Nitro-2-toluonitrileHCID 78373Dimethylformamide dimethyl acetal

Product 1

HCID 866574742-Formyl-6-nitrobenzonitrileYield 19%

Reagents, catalysts & solvents 2

HCID 6228DimethylformamideSolventHCID 8028TetrahydrofuranSolvent

Conditions

Temperature
130 °C

Procedure

1,1-Dimethoxy-N,N-dimethylmethanamine (13.56 mL, 102 mmol) was added to a solution of 2-methyl-6-nitrobenzonitrile (15.0 g, 92.5 mmol) in anhydrous DMF (60 mL) under nitrogen and was heated at 130° C. for 15 h. Ice water (300 mL) was added, and the resultant dark precipitate was collected by filtration and dried under vacuum. Phosphate buffer (pH 7, 350 mL) and then NaIO4 (40 g, 187 mmol) were added to a solution of the dark precipitate in THF (350 mL) and stirred at rt for 3 h. The mixture was extracted with EtOAc, the combined extract was washed with brine and dried with MgSO4. The filtrate was concentrated and the residue was purified by chromatography on silica using the solvent gradient hexanes→EtOAc, to give 3.07 g (19%) of the title compound as a yellow solid. 1H NMR (400 MHz, DMSO-d6) δ 8.15 (t, J=8.4 Hz, 1H), 8.41 (dd, J=1.2, 7.6 Hz, 1H), 8.62 (dd, J=1.2, 8.4 Hz, 1H), 10.25 (s, 1H).

Workup

  1. filtrationthe resultant dark precipitate was collected by filtration
  2. customdried under vacuum
  3. extractionThe mixture was extracted with EtOAc
  4. extractionthe combined extract
  5. washwas washed with brine
  6. dry with materialdried with MgSO4
  7. concentrationThe filtrate was concentrated
  8. customthe residue was purified by chromatography on silica using the solvent gradient hexanes→EtOAc

Sources & evidence

ORD record
ord-c9150c4a039244189cb633e284c34382
Source dataset
uspto-grants-2014_01
Patent number
US08633186B2

Linked notes

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