2,6-Lutidine → 4-Formyl-2-methoxybenzonitrile

HRID 1480531Notes

Reaction equation

HRID 1480531 reaction equation
[CH:1]([C:3]1[CH:8]=[CH:7][C:6]([C:9]#[N:10])=[C:5]([O:11][CH3:12])[CH:4]=1)=C.N1C(C)=CC=CC=1C.I([O-])(=O)(=O)=[O:22].[Na+]>O1CCOCC1.O.[Os](=O)(=O)(=O)=O>[C:9]([C:6]1[CH:7]=[CH:8][C:3]([CH:1]=[O:22])=[CH:4][C:5]=1[O:11][CH3:12])#[N:10]

Participants

7

Reactant 3

HCID 79372,6-LutidineHCID 23667635Sodium periodateHCID 897251371-Vinyl-4-cyano-3-methoxybenzene

Product 1

HCID 600485344-Formyl-2-methoxybenzonitrile

Reagents, catalysts & solvents 3

HCID 30318Osmium TetroxideCatalystHCID 962WaterSolvent2×HCID 312751,4-DioxaneSolvent

Procedure

To a solution of 1-vinyl-4-cyano-3-methoxybenzene (0.343 g, 2.16 mmol, 1.0 eq) in dioxane (7 mL) was added 2,6-lutidine (0.461 g, 0.50 mL, 4.31 mmol, 2.0 eq) followed by osmium tetroxide (1.37 g, 1.32 mL of a 4% solution in water, 0.22 mmol, 0.1 eq). A brown/black solution resulted after 1→2 minutes. Sodium periodate (1.847 g, 8.63 mmol as a solution in 7 mL of water, 4.0 eq) was added forming a white precipitate. The mixture was stirred at room temperature for 35 minutes before partitioning between EtOAc (100 mL) and HCl (1M, 100 mL). The organics were washed with brine (100 mL), dried (Na2SO4) and concentrated under reduced pressure. MPLC (10→50% EtOAc-hexane) yielded the title compound as a white solid; 1H nmr (CDCl3) d 9.89 (1H, s, CHO), 8.09 (2H, m, ArH-2, H-6), 7.12 (1H, d, J 9.5 Hz, ArH-3), 4.04 (3H, s, OCH3); m/z 162 [M+H]+.

Workup

  1. customA brown/black solution resulted after 1→2 minutes
  2. customforming a white precipitate
  3. custombefore partitioning between EtOAc (100 mL) and HCl (1M, 100 mL)
  4. washThe organics were washed with brine (100 mL)
  5. dry with materialdried (Na2SO4)
  6. concentrationconcentrated under reduced pressure

Sources & evidence

ORD record
ord-a98e4f3c9b5c4b819de8d652cd3cc29e
Source dataset
uspto-grants-2016_08
Patent number
US09409884B2

Reaction notes

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