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- Heteroaromatic benzyl ethers as intermediates for palladium-catalysed transfer hydrogenolysis of benzyl alcoholsPublication . Araujo, Nuna C. P.; Brigas, Amadeu; Cristiano, Maria Lurdes Santos; Frija, L.; Guimarães, Emanuel M. O.; Loureiro, Rui M. S.A chemoselective and easy to carry procedure for the hydrogenolysis of benzyl alcohols is described. Benzyl alcohols are readily converted into tetrazolyl and benzisothiazolyl ethers that can be catalytically hydrogenolysed to toluenes over palladium-on-charcoal using hydrogen donors. The effect of electronwithdrawing heteroaromatic substituents is interpreted on the basis of chrystallographic structure determinations and molecular orbital calculations.
- Structural effects on sigmatropic shifts in heteroaromatic allyl ethersElectronic supplementary information (ESI) available: selected crystal data for compound 7. See http://www.rsc.org/suppdata/p1/b1/b102674g/Publication . Araujo, Nuna C. P.; Barroca, Pedro M. M.; Bickley, Jamie F.; Brigas, Amadeu; Cristiano, Maria Lurdes Santos; Johnstone, Robert A. W.; Loureiro, Rui M. S.; Pena, Paula C. A.In contrast to the known thermal, exclusively [3,3], O- to N- rearrangement of allyl groups in phenyltetrazoles (1, Scheme 1), the comparable migration of the allyl group in pseudosaccharyl ethers (3; Scheme 2) has been shown to proceed through both [1,3]- and [3,3]-mechanisms, 4, 5; for the pseudosaccharyl derivative of the natural product myrtenol (6; Scheme 3) only the product 7 of a [1,3]-shift has been observed; crystallographic data and theoretical calculations provide an explanation of this ease of [1,3]-isomerization and the observed selectivity as being due to conformational constraints and electronic factors.
- Kinetic study of Friedel-Crafts acylation reactions over hierarchical MCM-22 zeolitesPublication . Aleixo, Rodrigo; Elvas-Leitao, Ruben; Martins, Filomena; Carvalho, Ana P.; Brigas, Amadeu; Martins, Angela; Nunes, NelsonFriedel-Crafts acylation was studied under mild conditions using hierarchical MCM-22 zeolites prepared by desilication and by desilication + acid treatment, using furan, pyrrole and anisole as substrates, and acetic anhydride as acylating agent. Enhanced catalysis was observed for furan and anisole, especially at short reaction times. Kinetic results modelling using non-linear regressions applied to a simplified Langmuir-Hinshelwood equation showed that desilication treatment followed by acid treatment improved kinetics (higher k and TOF). A QSPR methodology using nine substrate and zeolite descriptors was applied to model kinetics and adsorption. For both processes, the best QSPR model equations lead to the same descriptors, namely, Bronsted acidity, as zeolite's feature, and both van der Waals volume and Dimroth-Reichardt E-T(N) parameter (related to dipolarity and Lewis acidity) as substrates' characteristics. Normalization of descriptors allowed quantification of each descriptor's relative importance leading to a better understanding of the catalytic and adsorption processes. (C) 2017 Elsevier B.V. All rights reserved.
- Regioselectivity in hetero diels-alder reactionsPublication . Grosso, Carla; Liber, Marta; Brigas, Amadeu; Pinho e Melo, Teresa M. V. D.; Lemos, AmericoRegioselectivity in hetero Diels-Alder reactions can be observed in a simple reaction between a nonsymmetrical heterodiene and an unsymmetrical heterodienophile. A 9 h and easy to implement laboratory experiment is described, in which students can observe the regioselectivity of inverse "electron-demand" hetero Diels-Alder reactions of an azoalkene with furan or 2,3-dihydrofuran acting as dienophile. This experiment combines synthesis, structural analysis (IR spectroscopy and NMR spectroscopy), and dry- and vacuum-flash isolation methods.
- [4+2] Cycloadditions of 3-Tetrazolyl-1,2-diaza-1,3-butadienes: synthesis of 3-Tetrazolyl-1,4,5,6-tetrahydropyridazinesPublication . Lopes, Susana M. M.; Brigas, Amadeu; Palacios, Francisco; Lemos, A.; Melo, Teresa M. V. D. Pinho eThe synthesis of new 3-tetrazolyl-1,4,5,6-tetrahydropyridazines by Diels–Alder reactions of ethyl 3-(tetrazol-5-yl)-1,2- diaza-1,3-butadiene-1-carboxylates is reported. These 1,2- diaza-1,3-dienes reacted with electron-rich heterocycles, nucleophilic olefins and cumulenes, as well as with electrondeficient dienophiles, to give the target compounds regioselectively. Computational studies corroborated the rationalization of the observed reactivity and selectivity.
- Composition and in vitro antioxidants activity of Chamaerops Humilis L.Publication . Coelho, Jose P.; Veiga, Jerson G.; Elvas-Leitao, Ruben; Brigas, Amadeu; Dias, Ana M.; Oliveira, Maria C.; Morgado, M.; Bernardes, R.; Amador, M.; Afonso, P. M.The aim of this work is to evaluate the polyphenols composition and the antioxidant activity of methanol extracts of Chamaerops humilis L. Methanol extracts from dried leaves of Chamaerops humilis were prepared using Soxhlet extraction and examined as potential sources of phenolic compounds. Different methods were used to evaluate antioxidant activity of the extracts, including colored (ABTS*+), DPPH radical scavenging assay and reducing power. Total phenolic and flavonoid contents of the extracts were evaluated by Folin-Ciocalteu and aluminum chloride (AlCl3) methods, respectively. Phenolic compositions of the methanol extracts were elucidated by high performance liquid chromatography coupled on-line with tandem mass spectrometry (HPLC-MS/MS). The extract was mainly composed of C-and O-flavones and its O-methylated derivatives. The results suggest that methanol extracts have good potential as sources of bioactive compounds and presents an important antioxidants capacity, which can ensures its potential recommendation for application in the pharmaceutical and nutraceutical sectors.
- Natural deep eutectic solvents in the hetero-Diels-Alder approach to bis(indolyl)methanesPublication . Grosso, Carla; Brigas, Amadeu; de los Santos, Jesus M.; Palacios, Francisco; Lemos, Americo; Pinho e Melo, Teresa M. V. D.For the first time, the use of natural deep eutectic solvents (NADES) as reaction media to carry out hetero-Diels-Alder reactions is disclosed. This allowed to improve the efficiency and sustainability of the synthetic approach to bis(indolyl)methanes (BIMs) based on bis-hetero-Diels-Alder/conjugate addition reactions of nitroso- and azoalkenes with indoles. The ternary mixture of H2O with choline chloride/glycerol allowed the tuning of the physical properties of this NADES leading to a better solvent system, affording the target hydroxyiminomethyl- and hydrazonomethyl-BIMs, in much shorter reaction times, higher efficiency and easier isolation procedures. Furthermore, the direct access to carbonyl-BIMs was possible when 3-methyl-1-tert-butoxycarbonyl azoalkenes were used. [GRAPHICS] .
- Thermal rearrangement of 3-allyloxy-1,2-benzisothiazole 1,1-dioxides: an unusual inversion of products of sigmatropic [3,3]-shift to give the [1,3]-IsomersPublication . Cristiano, Maria Lurdes Santos; Brigas, Amadeu; Johnstone, Robert A. W.; Loureiro, Rui M. S.; Pena, Paula C. A.3-Allyloxy-1,2-benzisothiazole 1,1-dioxides isomerize thermally to give [3,3]- and [1,3]-products 6 of sigmatropic shift, of which the former reacts further to give solely the [1,3]-isomer.
- Mild liquid-phase Friedel-Crafts acylation of heteroaromatic compounds over zeolite BetaPublication . Álvaro, V. F. D.; Brigas, Amadeu; Derouane, E. G.; Lourenço, J. P.; Santos, Bruna S.Heteroaromatic compounds, such as thiophenes, pyrroles and furans, were acylated using zeolite Beta, with and without modifications, and acetic anhydride. Amenable conditionswere found to carry out these acylations in high yield, sometimes in a very short time (10 min). Indium modified catalyst have provided a way of attaining good yields in the acylation of pyrrole.
- Zooming in with QSPR on Friedel-Crafts acylation reactions over modified BEA zeolitesPublication . Aleixo, Odrigo; Elvas-Leitao, Ruben; Martins, Filomena; Carvalho, Ana P.; Brigas, Amadeu; Nunes, Ricardo; Fernandes, Auguste; Rocha, Joao; Martins, Angela; Nunes, NelsonThe catalytic behaviour of hierarchical BEA zeolites with Si/Al ratio of 12.5 and 32 was studied in Friedel-Crafts acylation reactions using furan, anisole and pyrrole as substrates and acetic anhydride as acylating agent. Hierarchical BEA samples were submitted to alkaline and alkaline + acid treatments. Kinetic modelling using nonlinear regressions applied to a simplified Langmuir-Hinshelwood equation showed that the Si/Al ratio of the parent materials strongly influenced the catalytic behaviour. Catalytic results were correlated with physicochemical properties using a Quantitative Structure-Property Relationship (QSPR) methodology. This approach provided detailed information about the role of key properties on the catalytic behaviour, and pointed out which properties should be modified through direct synthesis and/or post-synthesis treatments to obtain materials with optimized catalytic performance.