Synthesis and surface properties of chemodegradable anionic surfactants: Diastereomeric (2‐n‐alkyl‐1,3‐dioxan‐5‐yl) sulfates with monovalent counter‐ions

Abstract

Sodium, potassium and ammonium cis-and trans-(2-n-alkyl-1,3-dioxan-5-yl) sulfates 6-8 (alkyl: n-C 9 H 19 , 6a-8a, and n-C 11 H 23 , 6b-8b) were synthesized in a reaction of aliphatic aldehydes 1a,b with glycerol 2 followed by separation in high yields of individual geometric isomers of cis-and trans-2-n-alkyl-5-hydroxy-1,3-dioxanes, cis-3a,b and trans-3a,b, followed by sulfation with sulfur trioxide-pyridine complex, and finally neutralization with NaOH, KOH, and NH 4 OH, respectively. Physical data of the compounds and some surface properties of 2-nnonyl derivatives, such as critical micelle concentration (CMC), effectiveness of aqueous surface tension reduction (Π CMC ), surface excess concentration (Γ CMC ), and the surface area demand per molecule (A CMC ), were determined. It was shown that the surface activity of these compounds is influenced both by their geometric structure and by the monovalent counter-ion.Paper no. S1164 in JSD 3, 59-65 (January 2000). KEY WORDS:Aliphatic aldehyde, (2-n-alkyl-1,3-dioxan-5-yl) sulfate, 2-n-alkyl-5-hydroxy-1,3-dioxane, cis-trans isomerism, critical micelle concentration, 1,3-dioxane derivative, surface activity.World resources of glycerol obtained primarily from renewable natural oleochemicals are only partly utilized. This is a good motivation for using glycerol for syntheses of high-performance surfactants that are environmentally friendly. Surface-active compounds containing an acetal group are the largest group of chemodegradable surfactants (1-8). They are susceptible to hydrolytic decomposition and are biodegradable (9). Recently, we devised a convenient and simple method for isolating long-chain cisand trans-2-alkyl-5-hydroxy-1,3-dioxanes from four-component mixtures of glycerol acetals (10), i.e., reaction products of long-chain aliphatic aldehydes and glycerol. These hydrophobic intermediates are useful for the synthesis of sulfate-type anionic surfactants with high surface activity. Surface-active 2,5-disubstituted-1,3-dioxane derivatives also are model surfactants with defined chemical and geometric structures used for investigations of the effects of hydrophilic (11-13) or hydrophobic (8) substituent configuration on surface activity.In previous papers, we reported a relationship between surface activity and configuration of the anionic polar group joined to the C-5 carbon atom of the 1,3-dioxane ring: sulfate group in micelle-forming sodium cis-and trans-(2-n-alkyl-1,3-dioxan-5-yl) sulfates (13); methyl sulfate group in sodium cis-and trans-(2-n-undecyl-1,3-dioxan-5-yl)methyl sulfates (14); propanesulfonate group in sodium cis-and trans-3- [(2-n-undecyl-1,3-dioxan-5-yl)oxy]propanesulfonates (14); and carboxylate group in sodium cis-(15) and trans-(2-n-alkyl-5-methyl-1,3-dioxan-5-yl)carboxylates (Piasecki, A., and P. Ruchal / a, unpublished data).Formation of an ionic micelle from monomeric ions results from a balance between hydrophobic interactions of the amphipathic micelle-forming ions and electrostatic interactions between charged hydrophilic parts, as we...

Fluorescence Spectroscopy Study on the Interaction of Acetal Cleavable Anionic Surfactants and Bovine Serum Albumin

“…The anionic surfactants (SNPS and SNDPS) were synthesized using the procedures (Scheme 1) defined in the literature [24,25].…”

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Green Synthesis of Double Long‐Chain Diglycerol Diacetal and Its Application as Lubricating Base Oil

“…With the direction of modern surfactant science to design of green, biodegradable and sustainable surfactants, use of renewable feedstock and utilization of green synthetic approaches has been prevalent in the synthesis of novel green surfactants nowadays [22]. Use of glycerol acetals, produced from glycerol with long-alkyl-chain aldehydes, as hydrophobic intermediates for the synthesis of chemodegradable surfactants has received considerable attention in previous papers [23][24][25]. Recently, our group has become particularly interested in the green acetalization of glycerol with fatty aldehydes.…”

Preparation and Properties of Novel Double-Chain Nonionic Surfactants with Acid Decomposition Function

“…Therefore, chemocleavable surfactants, which decompose to give nonsurface-active species or other surfactants with different properties after fulfi lling their original functions, have become the focus of great interest in the fi eld of surfactant chemistry. In particular, many reports exist concerning the acid-decomposition types of amphiphilic compounds [1][2][3][4][5][6][7][8][9] .…”