p-Toluenesulfonic acid → 2-Formyl-5,5-dimethyl-1,3-dioxane

Participants

Reaction Steps

Streamlined Synthesis of 5-(5,5-Dimethyl-1,3-dioxan-2-yl)dipyrromethane (2). A mixture of glyoxal (10.0 g of 40 wt. % aqueous solution, 0.070 mol), 2,2-dimethyl 1,3-propanediol (7.28 g, 0.070 mol) and p-toluenesulfonic acid (0.260 g, 1.36 mmol) in benzene (140 mL) was refluxed for 4 h in a flask fitted with a Soxhlet extractor containing Na2SO4. Then the reaction mixture was treated with solid NaHCO3 (0.250 g, 2.90 mmol) and filtered. The filtrate was concentrated, affording crude 2-formyl-5,5-dimethyl-1,3-dioxane (1). The crude 1 was treated with pyrrole (223 mL, 3.45 mol; an amount corresponding to an assumed yield of 50% for the glyoxal monoacetal) and the standard reaction for dipyrromethane formation20 was carried out. InCl3 (0.762 g, 3.45 mmol) was added and the mixture was stirred under argon at room temperature for 1.5 h. The reaction mixture was worked up by addition of NaOH (4.13 g, 103 mmol), filtration, recovery of excess pyrrole from the filtrate, trituration of the resulting residue with hexanes to remove traces of pyrrole, and chromatography [silica, hexanes/CH2Cl2/ethyl acetate (7:2:1)], affording a pale yellow solid (2.84 g, 32%): mp 112-114° C.; 1H NMR δ 0.74 (s, 3H), 1.15 (s, 3H), 3.51 (d, J=11 Hz, 2H), 3.57 (d, J=11 Hz, 2H), 4.42 (d, J=2 Hz, 1H), 4.85 (d, J=2 Hz, 1H), 5.92 (m, 2H), 6.13 (m, 2H), 6.73 (m, 2H), 8.75 (s, 2H); Anal. Calcd for C15H20N2O2: C, 69.20; H, 7.74; N, 10.76. Found: C, 69.18; H, 7.77; N, 10.71.

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