4-Hydroxybenzaldehyde → 4-(6-Acetoxyhexyloxy)benzaldehyde

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Reaction Steps

An absorption spectrum was taken using the procedures described in Example 1 of the monomeric dipole 4-(6-hydroxyhexyloxy)-4-methylsulfonylstilbene, which has the structural formula: ##STR63## and was prepared as follows: First, 4-(6-acetoxyhexyloxy)benzaldehyde was prepared as follows: A mixture of 81.0 g (0.66 mol) of 4-hydroxybenzaldehyde, 99.7 g (0.73 mol) of 6-chloro-1-hexanol, 70.3 g (0.66 mol) of sodium carbonate, 49.7 g (0.33 mol) of sodium iodide, and 250 mL of 2-butanone was stirred mechanically and heated at reflux for 72 hours. The cooled reaction mixture was filtered, and the solvent was removed at reduced pressure to deposit the 4-(6-hydroxyhexyloxy)benzaldehyde as a brown oil. This oil was dissolved in 200 mL of pyridine, and 74.3 g (0.73 mol) of acetic anhydride was added dropwise with stirring. After the addition was completed, the reaction mixture was heated at reflux for 6 hours, and then cooled to room temperature. The mixture was poured onto 500 mL of water, and the product was extracted into dichloromethane (3 times using 250 mL each time). The combined organic extracts were washed successively with 5% aqueous HCl (2 times using 250 mL each time), and with saturated aqueous NaCl (250 mL). The organic layer was dried over MgSO4, was filtered, and the solvent was removed. The tan oily residue was fractionally distilled at reduced pressure, collecting the product 4-(6-acetoxyhexyloxy)-benzaldehyde at 190°-224° C. and pressure of 0.04 mm. The yield was 84.2 g, which is 48% of theoretical. Proton NMR was performed as in the Examples. 1H NMR (CDCl3) δ: 1.4 (m, 4H), 1.6 (m, 2H), 1.75 (m, 2H), 2.00 (s, 3H), 4.0 (m, 4H), 6.92 (d, 2H), 7.78 (d, 2H), 9.80 (s, 1H).

Provenance & Evidence