4-Methylmorpholine → 7,8-Methylenedioxy-4-chromanone

HRID 1534532Notes

Reaction equation

HRID 1534532 reaction equation
[CH2:1]1[O:9][C:8]2[C:3](=[C:4]([OH:10])[CH:5]=[CH:6][CH:7]=2)[O:2]1.CN1CCOCC1.[C:18](OCC1C=CC=CC=1)(=[O:21])[C:19]#[CH:20]>C1COCC1>[CH2:1]1[O:2][C:3]2[C:8](=[CH:7][CH:6]=[C:5]3[C:4]=2[O:10][CH2:20][CH2:19][C:18]3=[O:21])[O:9]1

Participants

5

Reactant 3

HCID 79724-MethylmorpholineHCID 543064Benzyl propiolateHCID 5867271,3-Benzodioxol-4-ol

Product 1

HCID 197805487,8-Methylenedioxy-4-chromanone

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent

Procedure

To a solution of 2,3-methylenedioxyphenol (27 g) and N-methyl morpholine (19.6 g) in THF (100 ml) was added benzyl propiolate (38 g) over a period of 30 minutes with cooling. After the addition was complete the reaction was stirred at room temperature for 1.5 hours followed by concentration. The residue was taken up into Et2O (500 ml), washed with 10% HCl (2×100 ml), dried over MgSO4. filtered and concentrated. This material was subjected to hydrogenation with 10%Pd/C in methanol at 4 atm. The reaction was filtered and concentrated. The resulting saturated acid was dissolved into methanesulfonic acid (350 ml) and stirred for 24 hours. The reaction was poured onto ice and extracted with CH2Cl2. The organic layer was washed with saturated Na2CO3, dried over MgSO4, filtered and concentrated to provide the desired material.

Workup

  1. temperaturewith cooling
  2. additionAfter the addition
  3. concentrationfollowed by concentration
  4. washwashed with 10% HCl (2×100 ml)
  5. dry with materialdried over MgSO4
  6. filtrationfiltered
  7. concentrationconcentrated
  8. filtrationThe reaction was filtered
  9. concentrationconcentrated
  10. dissolutionThe resulting saturated acid was dissolved into methanesulfonic acid (350 ml)
  11. stirringstirred for 24 hours
  12. additionThe reaction was poured onto ice
  13. extractionextracted with CH2Cl2
  14. washThe organic layer was washed with saturated Na2CO3
  15. dry with materialdried over MgSO4
  16. filtrationfiltered
  17. concentrationconcentrated

Sources & evidence

ORD record
ord-b5bde6a34f0d4341ad31093ede501969
Source dataset
uspto-grants-1992_02
Patent number
US05089519

Reaction notes

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