Morpholine → 5,6,7-Trimethoxynaphthalene-2-carbaldehyde

HRID 279981Notes

Reaction equation

HRID 279981 reaction equation
[CH3:1][O:2][C:3]1[C:12]([O:13][CH3:14])=[C:11]([O:15][CH3:16])[CH:10]=[C:9]2[C:4]=1[CH:5]=[CH:6][C:7]([C:17](OC)=[O:18])=[CH:8]2.[H-].COCCO[Al+]OCCOC.[Na+].[H-].N1CCOCC1.[OH-].[Na+]>C1(C)C=CC=CC=1>[CH3:1][O:2][C:3]1[C:12]([O:13][CH3:14])=[C:11]([O:15][CH3:16])[CH:10]=[C:9]2[C:4]=1[CH:5]=[CH:6][C:7]([CH:17]=[O:18])=[CH:8]2

Participants

6

Reactant 4

HCID 8083MorpholineHCID 14798Sodium HydroxideHCID 623941Methyl 5,6,7-trimethoxynaphthalene-2-carboxylate2×HCID 21584525Sodium bis(2-methoxyethoxy)aluminiumhydride

Product 1

HCID 218916375,6,7-Trimethoxynaphthalene-2-carbaldehyde

Reagents, catalysts & solvents 1

HCID 1140TolueneSolvent4×

Procedure

Methyl 5,6,7-trimethoxynaphthalene-2-carboxylate (C. L. Chen, F. D. Hostettler, Tetrahedron, 1969, 25, 3223) was reduced to the aldehyde in the following manner. Sodium bis(2-methoxyethoxy)aluminium hydride in toluene (5.6 ml, 20 mmol, 70% solution) was chilled to -20° C. under nitrogen in 20 ml of dry toluene and then 1.74 ml (20 mmol) of morpholine in 5 ml of toluene was added dropwise to it. The reaction was allowed to stir at -5° for 30 minutes, after which it was rechilled to -20° and added slowly to a solution of methyl 5,6,7-trimethoxynaphthalene-2-carboxylate (2.76 g, 10 mmol) in 20 ml of toluene at -20°. The reaction was stirred for 30 minutes at -10°, then rechilled to -20°, basified with 20 ml (40 mmol) of 2N sodium hydroxide, and extracted with three times 25 ml of toluene. The combined toluene layers were washed with 50 ml of 1N hydrochloric acid, then with 50 ml of 0.5M sodium bicarbonate, and finally with 50 ml of water, and dried over magnesium sulfate, filtered and evaporated to give 2.55 g (52% crude yield) of the title compound. This was purified on a silica gel column eluting with hexane:ethyl acetate/12:1 to give 2.15 g (44%) of the product, m.p. 96°-98°. Anal. Calcd. for C14H14O4 : C, 68.28; H, 5.73. Found: C, 68.16; H, 5.78.

Workup

  1. customwas rechilled to -20°
  2. stirringThe reaction was stirred for 30 minutes at -10°
  3. customrechilled to -20°
  4. extractionextracted with three times 25 ml of toluene
  5. washThe combined toluene layers were washed with 50 ml of 1N hydrochloric acid
  6. dry with materialwith 50 ml of 0.5M sodium bicarbonate, and finally with 50 ml of water, and dried over magnesium sulfate
  7. filtrationfiltered
  8. customevaporated

Sources & evidence

ORD record
ord-57bbb383acac42eaad57cbc6b5fa4750
Source dataset
uspto-grants-1986_05
Patent number
US04587341

Reaction notes

Loading…