Acetalation and Ketalation Catalyzed by SO42-/TiO2-MoO3

The catalytic activities of SO42-/TiO2-MoO3 in synthesizing cyclohexanone ethylene ketal,cyclohexanone 1,2-propanediol ketal, 2-propyl-1,3-dioxolane, 4-methyl-2-isopropyl-1,3-dioxolane,2-isopropyl-1,3-dioxolane, 4-methyl-2-isopropyl-1,3-dioxolane, butanone ethy-lene ketal and butanone 1,2-propanediol ketal were reported. It has been demonstrated that SO42-/TiO2-MoO3 is an excellent catalyst. Various factors concerned in this reaction have been investigated. The optimum conditions have been found, that is, the molar ratio of aldehyde/ketone to alcohol was 1:1.5 or 1:1.3,the mass ratio of the catalyst used to the reactants was 0.25～1.5%, and the reaction time was 45～60 min. Under this conditions, the yield of cyclohexanone ethylene ketal is 82.7%, cyclohexanone 1,2-propanediol ketal is 83.4%, the yield of 2-propyl-1,3-dioxolane is 68.1%,4-methyl-2-isopropyl-1,3-dioxolane is 87.5%, the yield of 2-isopropyl-1,3-dioxolane is 70.7%,4-methyl-2-isopropyl-1,3-dioxolane is 82.5%, the yield of butanone ethylene ketal is 74.1%, and butanone 1,2-propanediol ketal is 94.9%.Some equation and experiment results concerned of the synthetic acetals or ketals were listed as follows.     

Production of biofuel additives by esterification and acetalization of bioglycerol

The current transition from petrochemical resources to biomass-derived platform molecules is in great demand for the development of synergies, scientific innovations and breakthroughs, and steep changes in the infrastructure of chemical industries. This article is focused on new opportunities for the production of biofuel additives from bioglycerol, which is obtained as waste and/or by-product from the current biodiesel industries. Here, we summarize the recent relevant processes for the production of biofuel additives from bioglycerol over various acid catalysts in two different pathways: (i) the esterification of bioglycerol with acetic acid, levulinic acid and other acids, and (ii) the acetalization of bioglycerol with acetone, furfural, benzaldehyde and other carbonyl compounds. It is evident that the synthesis of biofuel additives through esterfication and acetalization of bioglycerol is an important research area with imperative prospects for industrial applications.     

Reactions of S-Silyl Esters of Tetracoordinated Phosphorus Thioacids with Acetals and Ortho Esters

The reactions of S-trimethylsilyl esters of dithiophosphoric, diamidodithiophosphoric, aryldithiophosphonic, aryltrithiophosphonic, and arylamidodithiophosphonic acids with diethyl acetal of benzaldehyde and ortho formiate and acetate were studied. On the basis of these studies, new derivatives of tetracoordinated phosphorus thioacids were obtained.     

Chalcogeno-Morita-Baylis-Hillman Reaction of Chalcogenide-Enones with Carbonyl Compounds

Abstract

The Chalcogeno-Morita-Baylis-Hillman reaction was achieved by the reactions of 2-(methylchalcogeno)phenyl vinyl ketones with carbonyl compounds or acetals in the presence of BF₃· Et₂O. This reaction proceeds via the intramolecular Michael addition of the chalcogenide group to an enone moiety followed by the aldol reaction of the resulting chalcogenonio-enolate with an aldehyde. The reactions were worked up with triethylamine or saturated aqueous NaHCO₃ to give the α -methylene aldols (the Morita-Baylis-Hillman adducts).     

Improved Synthesis of 1-Bromo-3-buten-2-one

A convenient procedure for the synthesis of 1-bromo-3-buten-2-one, 4, from commercially available 2-ethyl-2-methyl-1,3-dioxolane, 1, is described. The procedure involves three reaction steps: (1) The acetal 1 is converted to 2-(1-bromoethyl)-2-bromomethyl-1,3-dioxolane, 2, by reacting 1 with elemental bromine in dichloromethane to yield 98% of 2. (2) Dehydrobromination of 2 with potassium tert-butoxide in tetrahydrofuran gives 2-bromomethyl-2-vinyl-1,3-dioxolane, 3, in 84–93% yield. (3) Removal of the acetal protection from 3 by formolysis for 6–10 h afforded 1-bromo-3-buten-2-one, 4, in 85–94% yield. A more rapid method is acid hydrolysis of 3 under microwave activation (100 °C, 8–10 min), by which 4 was obtained in 75% yield. Full experimental details are given.

Acetals: a new organocatalysis chemotype for one-pot enantioselective α-amination

Conditions are described for one-pot Brønsted acid and organocatalysed enantioselective α-amination of acetals and associated functionalities. Of the organocatalysts screened, proline tetrazole gave the highest ee, while aqueous monochloroacetic acid proved to be the best Brønsted acid activator regarding minimizing racemization and maximizing product yield. The reaction opens up the way for using masked carbonyl functionalities in organocatalysis.     

缩醛/缩酮的合成研究进展

醛/酮与醇或原甲酸酯进行亲核加成反应生成的产物缩醛/缩酮,是一类重要的有机化合物。在有机合成中,该反应也广泛用于醛/酮羰基的保护或者乙二醇的保护,因此,缩醛/缩酮的合成研究引起广泛的关注。本文根据反应体系的不同,从酸催化、电催化和光催化三个方面对近年来缩醛/缩酮的合成研究进展进行详细综述。期望该综述作为学生基础有机化学课程的课后拓展阅读内容,能加深学生对基础反应的理解,培养学生的科研创新思维。     

Acid-catalyzed intramolecular cyclization of N-(4,4-diethoxybutyl)sulfonamides as a novel approach to the 1-sulfonyl-2-arylpyrrolidines

Herein we report our studies on the acid-catalyzed cyclisation of N-(4,4-diethoxybutyl)sulfonamides at the presence of polyatomic phenols as an efficient one-pot approach to the synthesis of 1-sulfonyl-2-arylpyrrolidines from the acyclic precursors.     

Synthesis and characterization of novel spirooxazacamphorsultam derivatives

Derivatives of camphorsultam which contain novel spirooxazolidine and spirooxazine structures have been prepared in high yield and purity. Though it was expected that the ketone moiety would undergo acetal formation, the imine instead underwent reaction and was proven by X-ray crystallography and 2D NMR techniques. The initial ketone-containing derivatives were then reduced to produce exo-hydroxy analogs that have potential as a new family of chiral auxiliaries.     

Synthetic approach to pentacyclic quassinoids from communic acids, via ambracetal derivatives

Methyl (8R,13S)-8α,13:13,17-diepoxy-14,15-dinorlabdane-19-oate, easily prepared from communic acids, is a suitable intermediate for synthesizing pentacyclic quassinoids, because it enables the elaboration of the A ring and the further construction of the B-C-D ring system of these terpenoids. The cetal group is stable under the reaction conditions utilized during the elimination of the ester group and the introduction of the hydroxyl group on C-3. At the same time, it enables the regeneration of the methylketone and exocyclic double bond presented by methyl 13-oxo-14,15-dinorlabd-8(17)en-19-oate. The latter compound was previously used to construct the B-C-D-ring of these quassinoids.