Formaldehyde → 2-(4H-benzo[d][1,3]dioxin-7-yl)acetonitrile

HRID 17944Notes

Reaction equation

HRID 17944 reaction equation
OC1C=C([CH2:8][C:9]#[N:10])C=CC=1.[CH2:11]=[O:12].[OH2:13].[C:14]1([CH3:24])[CH:19]=[CH:18][C:17](S(O)(=O)=O)=[CH:16][CH:15]=1>C1(C)C=CC=CC=1>[O:12]1[C:15]2[CH:16]=[C:17]([CH2:8][C:9]#[N:10])[CH:18]=[CH:19][C:14]=2[CH2:24][O:13][CH2:11]1

Participants

5

Reactant 3

HCID 712FormaldehydeHCID 521998p-Toluenesulfonic acid monohydrateHCID 137810422-(3-Hydroxyphenyl)acetonitrile

Product 1

HCID 591662162-(4H-benzo[d][1,3]dioxin-7-yl)acetonitrileYield 47.9%

Reagents, catalysts & solvents 1

HCID 1140TolueneSolvent

Procedure

To a solution of (3-hydroxyphenyl)acetonitrile (75.0 g, 0.56 mol) in toluene (750 mL) was added paraformaldehyde (84.0 g, 2.80 mol) and toluene-4-sulfonic acid monohydrate (10.7 g, 56.0 mmol) at room temperature. The reaction mixture was heated at reflux for 40 minutes. Toluene was removed by evaporation. Water (150 mL) and ethyl acetate (150 mL) were added. The organic layer was separated and the aqueous layer was extracted with ethyl acetate. The combined organics were washed with brine, dried over anhydrous Na2SO4 and evaporated under vacuum. The residue was separated by preparative HPLC to give 2-(4H-benzo[d][1,3]dioxin-7-yl)acetonitrile (4.7 g, 5%). 1H NMR (300 MHz, CDCl3) δ 6.85-6.98 (m, 3H), 5.25 (d, J=3.0 Hz, 2H), 4.89 (s, 2H), 3.69 (s, 2H).

Workup

  1. temperatureThe reaction mixture was heated
  2. temperatureat reflux for 40 minutes
  3. customToluene was removed by evaporation
  4. additionWater (150 mL) and ethyl acetate (150 mL) were added
  5. customThe organic layer was separated
  6. extractionthe aqueous layer was extracted with ethyl acetate
  7. washThe combined organics were washed with brine
  8. dry with materialdried over anhydrous Na2SO4
  9. customevaporated under vacuum
  10. customThe residue was separated by preparative HPLC

Sources & evidence

ORD record
ord-909d7aa9f45b4b6587bf61feb026f72e
Source dataset
uspto-grants-2010_06
Patent number
US07741321B2

Reaction notes

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