Synthesis and Surface‐Active Properties of Uronic Amide Derivatives, Surfactants from Renewable Organic Raw Materials

Abstract

Short chemical syntheses were developed to produce a new set of surfactants from uronic acids derived from widely available raw materials. Three different strategies were used to synthesize uronic amide derivatives, the structures of which were totally characterized by spectrometric methods (IR, MS, 1 H-RMN and 13 C-RMN). The best one, using an acid chloride as the synthetic intermediate, furnished the expected amides as a mixture of anomers in 46-58% global yield. Surface-active properties (CMC, c cmc , C max , A min ) of homologous series of uronic acid N-alkylamides from C8 to C18 were also assessed. In general, these sugar-based surfactants exhibited good surface-activities, and appeared as valuable nonionic surfactants compared to octylphenol 9-10 ethylene oxide condensate, the most well-known nonionic surfactant. Increasing the alkyl chain length influenced the CMC values for both glucuronic and galacturonic N-alkylamide derivatives. The galacturonic N-alkylamides decreased c cmc at slower values than their counterpart's glucuronic N-alkylamides. AbbreviationsCOSY Correlation spectroscopy DCC Dicyclohexyl carbodiimide DMF Dimethyl formamide DMSO Dimethyl sulfoxide ESIMS Electrospray ionisation mass spectrometry HMBC Heteronuclear multiple bond correlation HSQC Heteronuclear single quantum correlation NOESY Nuclear Overhauser effect spectroscopy TLC Thin layer chromatography TMS Tetramethylsilane

Carbohydrate-Based Surfactants: Structure-Activity Relationships

“…High molecular mass nonionic, mono, esteramide, nonionic, multi, ester/amide, (Desai et Banat, 1997) (Hill &LeHen-Ferrenbach, 2009) nonionic, mono, ester (Hill &LeHen-Ferrenbach, 2009) nonionic, mono, amide (Laurent et al 2011) nonionic, di, ester-ether (Richel et al 2010) nonionic, mono, ether (Vulfson, 1990) …”

“…by migration of surfactant to the surface, is more convenient for short chain derivative surfactants (high solubility in water) whereas the Langmuir approach, determining π after spreading and compressing surfactant molecules at the surface, is rather appropriate for long chain derivative surfactants (low solubility in water). Surface activities of uronic acid derivatives may be evaluated in both dynamic and static/quasi-satic modes using a series of complementary techniques at room temperature comprised between 20-25°C (Razafindralambo et al, 1995;2009;2011).…”

“…A s f o r a l l monomeric surfactants, whatever their nature, the general trend is respected with uronic acid derivatives, that is, the longer the alkyl chain length, the lower the CMC of the uronate and uronamide derivatives (Blecker et al, 2002;Laurent et al, 2011). About dynamic surface properties, an optimum chain length of eleven carbon atom gives the best performance, regarding the adsorption time and the maximum reduction of the surface tension.…”

First Conjugates of the Diterpenoid Isosteviol and Glucuronic Acid

“…Less than 30 amides of glucuronic acid (glucuronamides) were reported. They included branched glycopeptidomimetics [5], glycolipids [6][7][8] including anionic surfactants that transported hydrophilic drugs through hydrophobic cell membranes [7], oligosaccharides [9], conjugates with chlorin and bacteriochlorin [10], and receptors of chiral carboxylate anions [11]. Esterification (as a rule, by methyl, allyl, and benzyl alcohols) of glucuronic acid is used only to protect the carboxylic acid during glucuronide synthesis [2][3][4].…”

“…These were a) a single-pot acetylation of 3 by acetic anhydride in the presence of I 2 with subsequent work up with MeOH [13]; b) acetylation of D-glucuronic acid by acetic anhydride in the presence of I 2 , isolation of anhydride 4, and its subsequent hydrolysis in THF [14,15]; and c) acetylation of D-glucuronic acid by acetic anhydride with an H 2 SO 4 (conc.) catalyst [8]. In the first method, the yields of tetraacetylated 5 were insignificant with the main product being its methyl ester.…”