Studio della reattività del glicerol carbonato nella sintesi di derivati fenolici

Supported by the increasing sustainable awareness, glycerol carbonate has gained much interest over the last 20 years because of its versatile reactivity and as a way to valorize waste glycerol. Numerous synthesis pathways for this molecule were identified, some of them very promising and on the verge of being applied at an industrial scale. Here, we report a study aimed at valorizing glycerol carbonate as chemical intermediate, in order to synthesize 2-hydroxymethyl-1,4-benzodioxane (HMB). This molecule finds important applications as key intermediate for the synthesis of a broad class of pharmaceuticals and therapeutic agents. Concerning the presence of a stereogenic center on the hydroxymethyl group, due to the pharmaceutical importance to obtain and isolate one single enantiomer, , nowadays HMB is obtained through batch scale process, using a multi-reaction approach and starting from reagents of the chiral pool. We carried out the reaction from a solution of glycerol carbonate and catechol 2:1. In the presence of a simple basic catalyst, at high temperatures, it was possible obtain total reactants conversion and high yield to HMB in few hours reaction time. Also, in the aim of developing a process which might adhere the principles of Green Chemistry, we avoided the use of solvents. Similar results were obtained using a 1:1 feed ratio of reactants, even if selectivity to HMB decrease, due to the presence of side reactions. A complete study of the reaction mechanism is proposed in this thesis.

One-pot synthesis of imines from benzyl alcohol and amines on Au/ZrO2 catalyst

Imines were synthesized from benzyl alcohol and amines by using catalysts of gold nanoparticles supported on ZrO2 (Au/ZrO2). The effects of reaction time, temperature, gold loadings and base were investigated. High yields were achieved under moderate conditions (60 °C) in the presence of KOCH3. For instance, the yield of N-benzylidenebenzylamine produced from benzyl alcohol and benzylamine on 3 wt% Au/ZrO2 is 87 %. The synthesis of imine involves two reaction steps: selective oxidation of benzyl alcohol to benzaldehyde and the coupling reaction of amines with benzaldehyde. In the first step, the base promotes the selective oxidation. The reactions of benzyl alcohol with three different amines, aniline, n-butylamine and benzylamine, were conducted to produce corresponding imines. The results show that the amine with stronger nucleophilicity has better ability to react with benzaldehyde in the second step, resulting in higher yield of the corresponding imine. We proposed a tentative mechanism for the synthesis process.

Graphene-nanocrystalline metal sulphide composites produced by a one-pot reaction starting from graphite oxide

Graphene-nanocrystalline metal sulphide composites were prepared by a one-pot reaction. A dispersion of graphite oxide layers in an aqueous solution of metal ions (Cd2+/Zn2+) was reacted with H2S gas, which acts as a sulphide source as well as a reducing agent, resulting in the formation of metal sulphide nanoparticles and simultaneous reduction of graphite oxide sheets to graphene sheets. The surface defect related emissions shown by free metal sulphide particles are quenched in the composites due to the interaction of the surface of the nanoparticles with graphene sheets.

One-pot synthesis of nidorellaurenal and its one-step conversion to methyl nidorellaurinate, a constituent of Nidorella auriculata

Nidorellaurenal (4) is obtained in a one-pot reaction, involving heating of the known carbinol (8) with selenium dioxide in dimethyl sulphoxide. Conversion of 4 to methyl nidorellaurinate (6), the natural product from Nidorella auriculata, has been achieved by Corey's one-step procedure.

One-Pot Synthesis of beta-Amino/beta-Hydroxy Selenides and Sulfides from Aziridines and Epoxides

Diaryl disulfides and diselenides undergo facile cleavage on treatment with rongalite (sodium hydroxymethanesulfinate) to generate the corresponding thiolate and selenolate species in Situ, which effect the ring opening of aziridines and epoxides in a regioselective manner. A simple, mild, cost-effective protocol has been developed to prepare beta-amino and beta-hydroxy sulfides and selenides in a one-pot operation.

One-pot protection and activation of amino acids using pentafluorophenyl carbonates

Protection of the amino group and activation of the carboxylic acid groups are the most important steps associated with any peptide synthesis protocol; hence, a one-pot process to achieve these is highly desirable. A possible strategy is to use pentafluorophenyl carbonates to simultaneously protect the amino group as a carbamate derivative and activate the carboxylic acid group as a pentafluorophenyl ester. A detailed study is carried out to understand the scope and limitations of this method using five different pentaflurophenyl carbonates. The efficiency of these one-pot reactions depends largely on the nature of the pentafluorophenyl carbonates and also on the nature of the amino acids. Electron deficient and sterically less demanding carbonates reacted faster than the others, whereas amino acids with longeraliphatic side chains gave better yields than more polar amino acids.

Facile one-pot synthesis of thio and selenourea derivatives: A new class of potent urease inhibitors

A facile, one-pot synthesis of thio and selenourea derivatives from amines using tetrathiomolybdate 1 and tetraseleno-tungstate 2 as sulfur and selenium transfer reagents, respectively, is reported. The compounds were tested for their activity as urease inhibitors and some of the compounds showed potent activity in the nanomolar range towards jack bean urease. (C) 2007 Elsevier Ltd. All rights reserved.

Synthesis of Unnatural Selenocystines and beta-Aminodiselenides via Regioselective Ring-Opening of Sulfamidates Using a Sequential, One-Pot, Multistep Strategy

A variety of N-alkyl-beta-aminodiselenides have been synthesized in high yield from sulfamidates under mild reaction conditions using potassium selenocyanate and benzyltriethylammonium tetrathiomolybdate ([BnNEt3](2)MoS4) in a sequential, one-pot, multistep reaction. The tolerance of multifarious protecting groups under the reaction conditions is discussed. The methodology was successfully extended to the synthesis of selenocystine,3,3'-dialkylselenocystine, and 3,3'-diphenylisoselenocystine and their direct incorporation into peptides.

One pot synthesis of polycyclic oxygen aromatics. Part III mechanism of formation

Reaction of 6-Image -butyl-1-bromomethyl-2-(2-tetrahydropyranyloxy)-naphthalene2c with tetrachlorocatechol (TCC) in acetone in presence of K2CO3 gave diastereomers 6c and 7c. A mechanism (Scheme-1) invoking the base induced cleavage of the pyranyl ether 2 to 1,2-naphthoquinone-1-methide 8 as the first step has been postulated. The cleavage of the pyranyl ether linkage in 2 to give dimers 4 and 5 of 1,2-naphthoquinone-1-methide has been demonstrated with different bases. 1,2-Naphthoquinone-1-methide 8, thus generated, undergoes Michael addition with TCC followed by elimination of chloride ions to give a diketone, which further undergoes aldolisation with acetone to give diastereomers 6 and 7. Michael reaction of 8, generated Image from pyranyl ethers 2a-c, with tetrabromocatechol (TBC) under similar-reaction conditions gave the expected monobromo compounds 6h, 6i, 6k, 7n, 7n and 7q. The last step in the proposed mechanism, Image ., aldolisation has also been demonstrated using different ketonic solvents. Thus, reaction of 2a-c with TCC/TBC in diethyl ketone/methyl ethyl ketone under similar reaction conditions gave the expected compounds 6 and 7.

A Vicarious One-Pot Transformation of a Fluorocyclitol to a Polycyclitol: Observation of a Formal 4-Fold Axial-Equatorial Epimerization on a Conformationally Locked Scaffold

A conformationally locked fluoropentol undergoes an interesting transformation to (trans,anti,trans,anti,trans)-perhydro-2,3,4a,6,7,8a-naphthalenehexol essentially under conditions of base-induced transesterification. The proposed rationale for the observed metamorphosis involves a nucleophilic displacement of fluoride, and subsequent stereo- and regioselective anti-Furst-Plattner-type ring-opening of the epoxide thus formed.

One pot synthesis of polycyclic oxygen aromatics. Part IV reaction of THP ether of 2-bromomethyl phenols

Reaction of 2-bromomethyl-1-(2′-tetrahydropyranyloxy) benzene 3a with tetrachlorocatechol(TCC) in acetone in presence of anhydrous K2CO3 resulted in the formation of diastereomeric products to which cis- & trans- 6-chloro-8-hydroxy-8-(2-oxopropyl)spiro[9H-benzo[a]xanthen- 9,2′(1′H) benzofuran]-7(8H)-one (7a & 8a) structures were assigned, along with tetrachlorocatechol ethers (5a & 6a). Similar reaction of 3a with tetrabromocatechol(TBC) gave the expected monobromo compounds 7d & 8d along with the ethers 5d & 6d. When the reaction was repeated with substrates 3b–c with TCC/TBC in ketonic solvents(acetone/methyl ethyl ketone), the corresponding compounds 5b–c to 8b–c, 5e–f to 6e–f, 7e–g & 8e–h were obtained. A suitable explanation has been given for the formation of acetonyl compound 6 in this reaction.

One pot conversion of alcohols to disulfides mediated by benzyltriethylammonium tetrathiomolybdate

A one pot conversion of alcohols to disulfides in good yields via the activation of a hydroxyl group with DCC or P(NMe2)(3) / CCl4 followed by treatment with benzyltriethylammonium tetrathiomolybdate is reported. (C) 1999 Elsevier Science Ltd. All rights reserved.

Sm(III)nitrate-catalyzed one-pot synthesis of furano3,2c]-1,2,3,4-tetrahydroquinolines and DNA photocleavage studies

The synthesis and DNA photocleavage studies of furano3,2-c]-1,2,3,4-tetrahydroquinolines have been reported. Sm(III)nitrate was found to be an efficient for the Diels-Alder reaction of aryl amines with 2,3-dihydrofuran to offer the corresponding furano3,2-c]-1,2,3,4-tetrahydroquinolines derivatives as a mixture of cis/trans stereoisomers in moderate yields. The aqueous solubility of acid catalyst can be recycled without significant loss of activity. The DNA photocleavage studies shows that, the cis/trans stereoisomers are good DNA cleavage mimic in terms of molecular structure. (C) 2012 Elsevier B.V. All rights reserved.

Vanadium pentoxide nanobelts: One pot synthesis and its lithium storage behavior

In this paper, we report a synthesis, characterization and electrochemical properties of V2O5 nanobelts. V2O5 nanobelts have been prepared via hydrothermal treatment of commercial V2O5 in acidic (HCl/H2SO4) medium at relatively low temperature (160 degrees C). The hydrothermally derived products have been characterized by powder X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FT-IR), Raman spectroscopy, X-ray photo electron spectroscopy (XPS), UV-Vis spectroscopy, Scanning/Transmission electron microscopy (SEM/TEM). XRD pattern of V2O5 nanobelts show an orthorhombic phase. From the FTIR spectrum, the peak observed at 1018 cm-1 is characteristic of the stretching vibration mode of the terminal vanadyl, V = O. The UV-Vis absorption spectrum of V2O5 nanobelts show maximum absorbance at 430 nm, which was blue-shifted compared to that of bulk V2O5. TEM micrographs reveal that the products consist of nanobelts of 40-200 nm in thickness and several tens of micrometers in length. The electrochemical analysis shows an initial discharge capacity of 360 mAh g-1 and its almost stabilized capacity is reached to 250 mAh g-1 after 55 cycles. A probable reaction mechanism for the formation of orthorhombic V2O5 nanobelts is proposed.

An efficient one-pot synthesis and photoinduced DNA cleavage studies of 2-chloro-3-(5-aryl-4,5-dihydroisoxazol-3-yl)quinolines

4,5-Dihydroisoxazoles continue to attract considerable interest due to their wide spread biological activities. Here, we identify an efficient protocol for the preparation of 4,5-dihydroisoxazoles (2-isaxazolines) (4a-g) from quinolinyl chalcones. The nucleolytic activities of synthesized compounds were investigated by agarose gel electrophoresis. All these compounds were showed the remarkable DNA cleavage activity (concentration dependent) with pUC19 DNA at 365 nm UV light. The DNA cleavage activity was significantly enhanced by the presence of iminyl and carboxy radicals of DIQ. (C) 2012 Elsevier Ltd. All rights reserved.