Acetalisation of bio-glycerol with acetone to produce solketal over sulfonic mesostructured silicas Abstract Sulfonic acid-functionalized mesostructured silicas

have demonstrated excellent catalytic behaviour in the acetalisation of glycerol with acetone to yield 2,2-dimethyl-1,3-dioxolane-4methanol, also known as solketal. This molecule constitutes an excellent compound for the formulation of gasoline, diesel and biodiesel fuels. The activity achieved with arenesulfonic acid-functionalized silica is comparable to that displayed by Amberlyst-15. Optimal production of solketal over arenesulfonic acid mesostructured silica has been established for a reaction system consisting of three consecutive 2-step batches (30 min under reflux and an evaporation step under vacuum), and using a 6/1 acetone/glycerol molar ratio. The use of lower grades of glycerol, such as technical (purity of 91.6 wt%) and crude (85.8 wt%) glycerol, has also provided high conversions of glycerol over sulfonic acid-modified heterogeneous catalysts (84% and 81%, respectively). For refined and technical glycerol the catalysts have been reused, without any regeneration treatment, up to three times, keeping the high initial activity. However, the high sodium content in crude glycerol deactivates the sulfonic acid sites by cation exchange. This deactivation is readily reversed by simple acidification of the catalyst after reaction.

Synthesis of Some Phenylpropanoid Monoglycerides via the Mitsunobu Protocol Abstract: Natural monoglycerides of cinnamic, ferulic and p-coumaric acids were synthesized in good to high overall yields from isopropylidene glycerol via the Mitsunobu reaction and further deprotection of the corresponding acetonides with Amberlyst 15. The method avoids the need of protection of the phenolic hydroxyls. During the Mitsunobu esterifications a strong influence of the acid strength on the efficacy and outcome of the reaction was observed. Keywords: phenylpropanoid glycerides, Mitsunobu esterification, deprotection.

Ketalization of glycerol to solketal in supercritical acetone Abstract In the last few years, the increasing production of biodiesel has led to an overproduction of glycerol, the main byproduct of this industry. This paper reports on the ketalization of glycerol in supercritical acetone to give solketal (4-hydroxymethyl-2,2-dimethyl-1,3dioxolane), an oxygenated compound useful as chemical and fuel additive for gasoline, diesel and biodiesel. The application of supercritical fluids (SCFs) in the chemical synthesis was explored to carry out reactions to obtain the above cyclic ketal. The experimental results reveal a drastic change in the reaction behavior when the critical condition of acetone is reached (T = 508 K). Below 508 K the reaction rate of solketal production is very low, but above this temperature a rapid increase in the reaction rate is observed. Finally, the reaction

rate is stabilized at 533 K and higher temperatures due to the conversion of glycerol to acrolein and polymeric products as side reactions. SintesisTrigliseridaRantaiSedang 1,2-Dikapril-3- Oleil-Gliserol Abstract: Trigliseridarantaisedang 1,2-dikapril-3-ofeil-gliserol telahdisintesisdarigliserolberturut-turutmelaluireaksiketalisasi, esterifikasi, deketalisasidanreesterifikasi. Gliseroldiketalisasidenganasetonuntukmenghasilkansolketal.Solketal yang terjadidiesterifikasidenganasamoleatmenghasilkansenyawa 2,2-dimetil 4-metil-oleil-1,3dioksolan. Selanjutnyasenyawainidideketalisasidenganasamklorida 1 N menghasilkan 3Oleil-gliserol.Kemudiansenyawainidireesterifikasidenganasamkapratmenghasilkan 1,2dikapril-3-oleil-gliserol. Senyawa yang terbentukpadasetiaptahapreaksidiidentifikasidenganspektroskopi FT-IR, 1H-NMR, dan 13CNMR. Abstract (other language): A medium chain triglyceride ( 1,2-dicapryl-3-oleoyl-glycerol) has been synthesized from glycerol via ketalization, esterification, deketalization, and reesterification reactions, respectively. Glycerol was ketalized with aceton to produce solketal. Solketal was esterified with oleic acid to produce 2,2-dimethyl-4-methyl-oleoyl-1,3dioxolane. Then this compound was deketalized with 1 N hydrochloric acid to obtain 3oleoyl-glycerol. This compound was reesterified with caprice acid to give 1, 2-dicapryl-3oleoyl-glycerol. The compound which produced in each step of reaction was identified by FTIR, 1H-NMR, dan 13C-NMR spectrometers. Synthesis of Solketal from Glycerol and Its Reaction with Benzyl Alcohol Abstract Due to the high growth of biodiesel production, glycerol, a major by-product from transesterification, is also produced at the same growing rate, resulting in its oversupply. This situation brings the price of glycerol to drop dramatically. Solketal, a derivative from glycerol, can be utilized by blending with gasoline or biodiesel as an additive. This work studies the synthesis of solketal from glycerol and acetone using homogeneous acid catalyst. The reaction progresses successfully when using the acetone in excess. Subsequently, the prepared solketal is used for synthesizing benzyl solketal ether by performing reaction with benzyl alcohol. However, several other products such as benzyl glycerol ether, dibenzyl ether and glycerol are formed. It was found that the high ratio of solketal to benzyl alcohol is required to increase selectivity toward benzyl solketal ether. 2011 Published by Elsevier Ltd. All rights reserved. Keywords: Glycerol; Solketal; Benzyl alcohol; Benzyl solketal ether

Polyesters based on Solketal derivatives for controlled release of herbicides Abstract Monomeric Solketal derivatives containing 2,4-dichlorophenoxyacetic and 4-chloro-2methylphenoxyacetic acids have been prepared, followed by polycondensations with dicarboxylic acids, such as resorcinol and hydroquinoldiacetic acids, and adipic acid, to give the corresponding linear polyesters. Crosslinked polymers were also prepared by reacting the linear polyesters produced with different ratios (5% and 10% by weight) of HMDI. In addition, investigation of the hydrolysis rates of the polymers obtained was undertaken under different simulated conditions, such as of pH and temperature. The amounts of herbicide released were evaluated by measuring the UV absorbance of the supernatant solution at different points in time. Kinetic resolution of (R,S)-1,2-isopropylidene glycerol (solketal) ester derivatives by lipases Abstract A study on the enantioselective hydrolysis of (R,S)-1,2-isopropylidene glycerol (4hydroxymethyl-2,2-dimethyl-1,3-dioxolane, solketal) octanoate catalyzed by different lipases was carried out. Among them, Pseudomonas sp. lipase proved to be the most effective. It was shown that the ester bearing the longer octanoyl acyl chain is a more suitable substrate for this lipase compared to the acetate counterpart. By properly combining enzyme load, temperature and reaction time, either the (S)-alcohol or the remaining ester could be obtained in moderate to high selectivities. Ethyl acetate was found to be the best solvent for the kinetic resolutions effected by such lipase but our results show that toluene may prove useful.