Acrylonitrile → 8-tert-butyl-2H-chromene-3-carbonitrile

HRID 1662132Notes

Reaction equation

HRID 1662132 reaction equation
[C:1]([C:5]1[C:6]([OH:13])=[C:7]([CH:10]=[CH:11][CH:12]=1)[CH:8]=O)([CH3:4])([CH3:3])[CH3:2].[C:14](#[N:17])[CH:15]=[CH2:16].N12CCN(CC1)CC2>[OH-].[Na+]>[C:1]([C:5]1[CH:12]=[CH:11][CH:10]=[C:7]2[C:6]=1[O:13][CH2:16][C:15]([C:14]#[N:17])=[CH:8]2)([CH3:4])([CH3:3])[CH3:2]

Participants

5

Reactant 3

HCID 7855AcrylonitrileHCID 9237DabcoHCID 36786753-tert-Butyl-2-hydroxybenzaldehyde

Product 1

HCID 666923318-tert-butyl-2H-chromene-3-carbonitrile

Reagents, catalysts & solvents 1

HCID 14798Sodium HydroxideSolvent

Procedure

3-tert-butyl-2-hydroxybenzaldehyde (Aldrich, 4.0 mL, 23.4 mmol), acrylonitrile (7.7 mL, 117 mmol), and 1,4-diazabicyclo[2.2.2]octane (0.66 g, 5.8 mmol) were heated in a microwave Personal Chemistry at 95° C. for 5 hours. Sodium hydroxide (1N, 200 mL) was added and the mixture was extracted twice with ethyl acetate (200 mL). The combined organic layers were washed with brine, dried over anhydrous sodium sulfate, filtered, and concentrate under reduced pressure. The residue was chromatographed on silica gel eluting with 0-to-30% ethyl acetate in hexane to afford the title compound. 1H NMR (300 MHz, DMSO-d6) δ ppm 1.31 (s, 9H), 4.85 (d, J=1.36 Hz, 2H), 6.97 (t, J=7.63 Hz, 1H), 7.16 (dd, J=7.63, 1.53 Hz, 1H), 7.29 (dd, J=7.80, 1.70 Hz, 1H), 7.58 (s, 1H). MS (DCI) m/z 231.10 (M+NH4)+.

Workup

  1. extractionthe mixture was extracted twice with ethyl acetate (200 mL)
  2. washThe combined organic layers were washed with brine
  3. dry with materialdried over anhydrous sodium sulfate
  4. filtrationfiltered
  5. concentrationconcentrate under reduced pressure
  6. customThe residue was chromatographed on silica gel eluting with 0-to-30% ethyl acetate in hexane

Sources & evidence

ORD record
ord-67282496824847c489dd322c11efd842
Source dataset
uspto-grants-2011_10
Patent number
US08030504B2

Reaction notes

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