Morpholine → 7,8-Dimethoxy-5-formyl-2H-1-benzopyran

HRID 280023Notes

Reaction equation

HRID 280023 reaction equation
[CH3:1][O:2][C:3]1[C:4]([O:17][CH3:18])=[C:5]2[O:10][CH2:9][CH:8]=[CH:7][C:6]2=[C:11]([C:13](OC)=[O:14])[CH:12]=1.[H-].COCCO[Al+]OCCOC.[Na+].[H-].N1CCOCC1.[OH-].[Na+]>C1(C)C=CC=CC=1>[CH3:1][O:2][C:3]1[CH:12]=[C:11]([CH:13]=[O:14])[C:6]2[CH:7]=[CH:8][CH2:9][O:10][C:5]=2[C:4]=1[O:17][CH3:18]

Participants

6

Reactant 4

HCID 8083MorpholineHCID 14798Sodium HydroxideHCID 12849831Methyl 7,8-dimethoxy-2H-1-benzopyran-5-carboxylateHCID 21584525Sodium bis(2-methoxyethoxy)aluminiumhydride

Product 1

HCID 128498327,8-Dimethoxy-5-formyl-2H-1-benzopyranYield 100.1%

Reagents, catalysts & solvents 1

HCID 1140TolueneSolvent2×

Procedure

Methyl 7,8-dimethoxy-2H-1-benzopyran-5-carboxylate (390 g, 1.56 mol) in toluene (1.6 L) was cooled to -15° and a solution of sodium bis(2-methoxyethoxy)aluminum hydride (908 mL, 3.5M in toluene, 3.18 mol) and morpholine (277 g, 3.18 mol) in toluene (900 mL) was added over a 45 min period. After stirring for an additional 30 min, 2N sodium hydroxide solution (2.85 L) was added. The organic layer was separated, washed with 0.8N hydrochloric acid (3×1 L), 5% sodium bicarbonate (500 mL) and water (1 L), dried (MgSO4) and concentrated to give 7,8-Dimethoxy-5-formyl-2H-1-benzopyran (344 g, 86%).

Workup

  1. customThe organic layer was separated
  2. washwashed with 0.8N hydrochloric acid (3×1 L), 5% sodium bicarbonate (500 mL) and water (1 L)
  3. dry with materialdried (MgSO4)
  4. concentrationconcentrated

Sources & evidence

ORD record
ord-3a7b2f6d8bfc4daea42d55e9926f9ede
Source dataset
uspto-grants-1986_05
Patent number
US04587342

Reaction notes

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