Notes- Acetals and Ketals of 1,3-Diols

Abstract

In no case did we obtain a product melting as low as -20°. The solutions for infrared work were obtained by dissolving the freshly prepared crystalline -hydroxyethyl peracetate in cold chloroform.Infrared spectra. A Baird-Atomic infrared spectrophotometer Model 4-55 was used in this work. The chloroform solution of peroxide was introduced immediately after preparation into the previously cooled low-temperature cell10 at 0°. A variable-path length cell was used in the reference beam to compensate for the chloroform absorption. A Teflon spacer cut from 0.020 mm. sheet was used in the cell since the normal lead spacer rapidly decomposed the peroxide.The decomposition of -hydroxyethyl peracetate at 0°to acetic acid was followed by allowing the solution to remain in the cell and scanning the carbonyl region periodically. Spectra of several reference compounds were obtained at ambient temperature except for acetaldehyde which was obtained at 0°. The compounds and the position (in microns) of their carbonyl bands are: peracetic acid (5.68); acetic acid (5.82); i-butyl peracetate (5.64); -butyl acetate (5.79); and acetaldehyde (5.80).Acknowledgment. We wish to thank Professor II. H. Wasserman of Yale University for helpful discussions and criticism, and to acknowledge the technical assistance of Mr.

Preparation and properties of sulfonate salt‐type cleavable surfactants with a 1,3‐dioxane ring

“…(2) is quite insoluble in almost all organic solvents, such as benzene. Conrad et aL (24) found that the reaction of aldehydes with 2 in benzene gave diacetals as the only products. Although 2 is quite soluble in diethylene glycol diethyl ether at its boiling point, the condensation reaction was slow, and a pure product was not isolated.…”

The Hydrolysis Equilibrium Effect of Water with Cu(II) Catalysts Used for the Selective Synthesis of Xylitol Monoacetals as Bio‐Based Surfactants

“…According to Hudson's results, the acetalization of xylitol with 37% aqueous formaldehyde can be efficiently carried out in the presence of hydrochloric acid, but the major product was the diacetal, which was obtained in 91% yield . The monoacetal from formaldehyde was obtained from the acid hydrolysis of the diacetal . Julnes reported the monoacetal could be obtained in 41.6% yield using xylitol and n ‐butanal in the presence of hydrochloric acid, but the n ‐butanal conversion and the monoacetal selectivity were not reported.…”

“…[16] The monoacetal from formaldehyde was obtained from the acid hydrolysis of the diacetal. [17,18] Julnes [19] reported the monoacetal could be obtained in 41.6% yield using xylitol and n-butanal in the presence of hydrochloric acid, but the n-butanal conversion and the monoacetal selectivity were not reported. The outcome using n-butanal was different to formaldehyde because of the larger amount of water (0.5 mol of reactant dissolved in 300 mL of water) used in the n-butanal reaction that was required for all of the reactants and products to be dissolved.…”

A Facile, Selective Preparation of Monoketals from Pentaerythritol and Ketones

“…In connection with the ketalization of pentaerythritol, numerous diketals have been reported. 10,11 However, an examination of the literature for the preparation of monoketals revealed that only few efforts have been made to obtain these synthetic intermediates, since Böeseken, 12 Orthner and Freyss, 13 and Orthner 14 published pioneer works regarding it. The extreme polarity of pentaerythritol and consequently its insolubility in almost all organic solvents appear to be the main difficulties found when dealing with the studies concerning the preparation of monoketals.…”

“…All available methods give low yields of monoketals. Conrad et al 10 have reported the preparation of monoketals from diketals by partial hydrolysis obtaining the monoketal of pentaerythritol and cyclohexanone in 12% yield. Schneider et al 11 have described methods for preparation of the mono and diketals of pentaerythritol in benzene-dioxane (1:1) as solvent, but neither yields nor selectivities towards both ketalization products have been reported.…”