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81.
Hossini I Harrad MA Ait Ali M El Firdoussi L Karim A Valerga P Puerta MC 《Molecules (Basel, Switzerland)》2011,16(7):5886-5895
Friedel-Craft acylation at 100 °C of 2,5,9,9-tetramethyl-6,7,8,9-tetrahydro-5H-benzocycloheptene [ar-himachalene], a sesquiterpenic hydrocarbon obtained by catalytic dehydrogenation of α-, β- and γ-himachalenes, produces a mixture of two compounds: (3,5,5,9-tetramethyl-6,7,8,9-tetrahydro-5H-benzocyclohepten-2-yl)-ethanone (2, in 69% yield), with a conserved reactant backbone, and 3, with a different skeleton, in 21% yield. The crystal structure of 3 reveals it to be 1-(8-ethyl-8-hydroperoxy-3,5,5-trimethyl-5,6,7,8-tetrahydronaphthalen-2-yl)-ethanone. In this compound O-H…O bonds form dimers. These hydrogen-bonds, in conjunction with weaker C-H…O interactions, form a more extended supramolecular arrangement in the crystal. 相似文献
82.
Oliveira FC Effenberger FB Sousa MH Jardim RF Kiyohara PK Dupont J Rubim JC Rossi LM 《Physical chemistry chemical physics : PCCP》2011,13(30):13558-13564
This work describes an easy synthesis (one pot) of MFe(2)O(4) (M = Co, Fe, Mn, and Ni) magnetic nanoparticles MNPs by the thermal decomposition of Fe(Acac)(3)/M(Acac)(2) by using BMI·NTf(2) (1-n-butyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide) or BMI·PF(6) (1-n-butyl-3-methylimidazolium hexafluorophosphate) ionic liquids (ILs) as recycling solvents and oleylamine as the reducing and surface modifier agent. The effects of reaction temperature and reaction time on the features of the magnetic nanomaterials (size and magnetic properties) were investigated. The growth of the MNPs is easily controlled in the IL by adjusting the reaction temperature and time, as inferred from Fe(3)O(4) MNPs obtained at 150 °C, 200 °C and 250 °C with mean diameters of 8, 10 and 15 nm, respectively. However, the thermal decomposition of Fe(Acac)(3) performed in a conventional high boiling point solvent (diphenyl ether, bp 259 °C), under a similar Fe to oleylamine molar ratio used in the IL synthesis, does not follow the same growth mechanism and rendered only smaller NPs of 5 nm mean diameter. All MNPs are covered by at least one monolayer of oleylamine making them readily dispersible in non-polar solvents. Besides the influence on the nanoparticles growth, which is important for the preparation of highly crystalline MNPs, the IL was easily recycled and has been used in at least 20 successive syntheses. 相似文献
83.
A method for the direct determination of Pb in wines by simultaneous multi-element atomic absorption spectrometry (SIMAAS) using a transversely heated graphite atomizer, Zeeman-effect background corrector and internal standardization is proposed. Bismuth was used as an internal standard and Pd(NO3)2 plus Mg(NO3)2 as chemical modifier to stabilize both the analyte and the internal standard. The implementation of two pyrolysis steps avoided any build-up of carbonaceous residues on the graphite platform. All diluted samples (1 + 1 v/v) in 0.2% v/v HNO3 and reference solutions (5.0-50 microg l(-1) Pb in 0.2% v/v HNO3) were spiked with 25 microg l(-1) Bi. For a 20 microl aliquot dispensed into the graphite tube, a good correlation (r = 0.9997) was obtained between the ratio of the analyte signal to the internal standard signal and the analyte concentration of the reference solutions. The electrothermal behaviour of Pb and Bi in red, white and rosé wines were compared. In addition, absorbance variations due to changes in experimental conditions, such as atomizer temperature, integration time, injected sample volume, radiation beam intensity, graphite tube surface, dilution and sample composition, were minimized by using Bi as internal standard. Relative standard deviations of measurements based on integrated absorbance varied from 0.1 to 3.4% and from 0.5 to 7.3% (n = 12) with and without internal standard correction, respectively. Good recoveries (91-104%) for Pb spikes were obtained. The characteristic mass was 45 pg Pb and the limit of detection based on integrated absorbance was 0.9 microg l(-1) Pb. Internal standardization increased the lifetime of the tube by 25%. Direct determinations of Pb in wines with and without internal standardization approaches were in agreement at the 95% confidence level. The repeatability and the tube lifetime were improved when using Bi as internal standard. The improvement in accuracy using an internal standard was only observed when the analytical results were affected by errors. 相似文献
84.
Thermolysis of a 2'-[(16)O]-O-benzoyl-[(17)O]-5'-O-(tert-butyldimethylsilyl)-O(2),3'-cyclouridine derivative gave the more stable 3'-[(17)O]-O-benzoyl-[(16)O]- 5'-O-(tert-butyldimethylsilyl)-O(2),2'-cyclouridine isomer, which was converted into 3'-[(17)O]-2'-azido-2'-deoxyuridine by deprotection and nucleophilic ring opening at C2' with lithium azide. The 5'-diphosphate was prepared by nucleophilic displacement of the 5'-O-tosyl group with tris(tetrabutylammonium) hydrogen pyrophosphate. Model reactions gave (16)O and (18)O isotopomers, and base-promoted hydrolysis of an O(2),2'-cyclonucleoside gave stereodefined access to 3'-[(18)O]-1-(beta-D-arabinofuranosyl)uracil. Inactivation of ribonucleoside diphosphate reductase with 2'-azido-2'-deoxynucleotides results in appearance of EPR signals for a nitrogen-centered radical derived from azide, and 3'-[(17)O]-2'-azido-2'-deoxyuridine 5'-diphosphate provides an isotopomer to perturb EPR spectra in a predictable manner. 相似文献
85.
Alicia Monleón Prof. Dr. Gonzalo Blay Prof. Dr. Luis R. Domingo Prof. Dr. M. Carmen Muñoz Prof. Dr. José R. Pedro 《Chemistry (Weinheim an der Bergstrasse, Germany)》2013,19(44):14852-14860
A very efficient synthesis of 5‐halogen‐1,3‐oxazin‐2‐ones has been accomplished by the halocyclisation reaction of chiral nonracemic N‐carbobenzyloxy (N‐Cbz)‐protected propargylic amines by using I2, Br2 and Cl2 as electrophile sources. The nature of the halogen influences the reaction time and yield. However, in all cases the reaction is totally regioselective taking place through a 6‐endo‐dig process regardless of the nature of the halogen and of the substituents in the starting material. To rationalise the experimental results, theoretical studies at the B3LYP/6‐311G* level have been performed. 相似文献
86.
Amnat Eamvijarn Nelson M. Gomes Tida Dethoup Jamrearn Buaruang Leka Manoch Artur Silva Madalena Pedro Ioulia Marini Vasilios Roussis Anake Kijjoa 《Tetrahedron》2013
Two new metabolites including a new aszonalenin analogue (1c) and a new meroditerpene (3) were isolated, together with aszonalenin (1a), acetylaszonalenin (1b), 13-oxofumitremorgin B (2), aszonapyrone A (4b) and helvolic acid, from the culture of the soil fungus Neosartorya fischeri (KUFC 6344). While the ethyl acetate extract of the culture of the diseased coral-derived fungus Neosartorya laciniosa (KUFC 7896) furnished aszonapyrone B (4a), aszonapyrone A (4b), tryptoquivaline L and 3′-(4-oxoquinazolin-3-yl) spiro[1H-indole-3,5′-oxolane]-2,2′-dione, the ethyl acetate extract of the culture of the marine sponge-associated fungus Neosartorya tsunodae (KUFC 9213) yielded a new analogue of chevalone C (5) and helvolic acid. The structures of the new compounds were established based on 1D and 2D NMR spectral analysis as well as HR-ESIMS. Compounds 1a–c, 2, 3, 4a, 4b and 5 were evaluated for their in vitro growth inhibitory activity on the MCF-7 (breast adenocarcinoma), NCI-H460 (non-small cell lung cancer) and A375-C5 (melanoma) cell lines by the protein binding dye SRB method. 相似文献
87.
Dicle Yardimci Dr. Pedro Serna Prof. Bruce C. Gates 《Chemistry (Weinheim an der Bergstrasse, Germany)》2013,19(4):1235-1245
The preparation of dinuclear rhodium clusters and their use as catalysts is challenging because these clusters are unstable, evolving readily into species with higher nuclearities. We now present a novel synthetic route to generate rhodium dimers on the surface of MgO by a stoichiometrically simple surface‐mediated reaction involving [Rh(C2H4)2] species and H2. X‐ray absorption and IR spectra were used to characterize the changes in the nuclearity of the essentially molecular surface species as they formed, including the ligands on the rhodium and the metal‐support interactions. The support plays a key role in stabilizing the dinuclear rhodium species, allowing the incorporation of small ligands (ethyl, hydride, and/or CO) and enabling a characterization of the catalytic performance of the supported species for the hydrogenation of ethylene as a function of the metal nuclearity and ligand environment. A change in the nuclearity from one to two Rh atoms leads to a 58‐fold increase in the catalytic activity for ethylene hydrogenation, a reaction involving unsaturated, but stable, dimeric rhodium species. 相似文献
88.
Díaz MC Illescas BM Martín N Viruela R Viruela PM Ortí E Brede O Zilbermann I Guldi DM 《Chemistry (Weinheim an der Bergstrasse, Germany)》2004,10(8):2067-2077
A new class of pi-extended TTF-type electron donors (11 a-c) has been synthesized by Wittig-Horner olefination of bianthrone (9) with 1,3-dithiole phosphonate esters (10 a-c). In cyclic voltammetry experiments, donors 11 a-c reveal a single, electrochemically irreversible oxidation-yielding the corresponding dicationic products-at relatively low oxidation potentials (approximately 0.7-0.8 V). Theoretical calculations, performed at the DFT level (B3 P86/6-31 G*), predict a highly-folded C(2h) structure for 11 a. In the ground state, the molecule adopts a double saddle-like conformation to compensate the steric hindrance. The calculations suggest that the intramolecular charge transfer associated with the HOMO-->LUMO transition is responsible for an absorption band observed above 400 nm. While the radical cation 11 a*+ retains the folded C(2h) structure predicted for the neutral molecule as the most stable conformation, the dication 11 a(2+) has a fully aromatic D(2) structure, formed by an orthogonal 9,9'-bianthryl central unit to which two singly-charged dithiole rings are attached. The drastic conformational changes that compounds 11 undergo upon oxidation account for their electrochemical properties. By means of pulse radiolysis measurements, radical-induced one-electron oxidation of 11 a-c was shown to lead to the radical cation species (11 a-c*+), which were found to disproportionate with generation of the respective dication species (11 a-c(2+)) and the neutral molecules (11 a-c). 相似文献
89.
Luminescent Di‐ and Trinuclear Boron Complexes Based on Aromatic Iminopyrrolyl Spacer Ligands: Synthesis,Characterization, and Application in OLEDs 下载免费PDF全文
Dr. D. Suresh Dr. Clara S. B. Gomes Patrícia S. Lopes Dr. Cláudia A. Figueira Bruno Ferreira Prof. Pedro T. Gomes Dr. Roberto E. Di Paolo Prof. António L. Maçanita Prof. M. Teresa Duarte Dr. Ana Charas Prof. Jorge Morgado Diogo Vila‐Viçosa Prof. Maria José Calhorda 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(25):9133-9149
New bis‐ and tris(iminopyrrole)‐functionalized linear (1,2‐(HNC4H3‐C(H)?N)2‐C6H4 ( 2 ), 1,3‐(HNC4H3‐C(H)?N)2‐C6H4 ( 3 ), 1,4‐(HNC4H3‐C(H)?N)2‐C6H4 ( 4 ), 4,4′‐(HNC4H3‐C(H)?N)2‐(C6H4‐C6H4) ( 5 ), 1,5‐(HNC4H3C‐(H)?N)2‐C10H6 ( 6 ), 2,6‐(HNC4H3C‐(H)?N)2‐C10H6 ( 7 ), 2,6‐(HNC4H3C‐(H)?N)2‐C14H8 ( 8 )) and star‐shaped (1,3,5‐(HNC4H3‐C(H)?N‐1,4‐C6H4)3‐C6H3 ( 9 )) π‐conjugated molecules were synthesized by the condensation reactions of 2‐formylpyrrole ( 1 ) with several aromatic di‐ and triamines. The corresponding linear diboron chelate complexes (Ph2B[1,3‐bis(iminopyrrolyl)‐phenyl]BPh2 ( 10 ), Ph2B[1,4‐bis(iminopyrrolyl)‐phenyl]BPh2 ( 11 ), Ph2B[4,4′‐bis(iminopyrrolyl)‐biphenyl]BPh2 ( 12 ), Ph2B[1,5‐bis(iminopyrrolyl)‐naphthyl]BPh2 ( 13 ), Ph2B[2,6‐bis(iminopyrrolyl)‐naphthyl]BPh2 ( 14 ), Ph2B[2,6‐bis(iminopyrrolyl)‐anthracenyl]BPh2 ( 15 )) and the star‐shaped triboron complex ([4′,4′′,4′′′‐tris(iminopyrrolyl)‐1,3,5‐triphenylbenzene](BPh2)3 ( 16 )) were obtained in moderate to good yields, by the treatment of 3 – 9 with B(C6H5)3. The ligand precursors are non‐emissive, whereas most of their boron complexes are highly fluorescent; their emission color depends on the π‐conjugation length. The photophysical properties of the luminescent polyboron compounds were measured, showing good solution fluorescence quantum yields ranging from 0.15 to 0.69. DFT and time‐dependent DFT calculations confirmed that molecules 10 and 16 are blue emitters, because only one of the iminopyrrolyl groups becomes planar in the singlet excited state, whereas the second (and third) keeps the same geometry. Compound 13 , in which planarity is not achieved in any of the groups, is poorly emissive. In the other examples ( 11 , 12 , 14 , and 15 ), the LUMO is stabilized, narrowing the gap between the highest occupied molecular orbital and the lowest unoccupied molecular orbital (HOMO–LUMO), and the two iminopyrrolyl groups become planar, extending the size of the π‐system, to afford green to yellow emissions. Organic light‐emitting diodes (OLEDs) were fabricated by using the new polyboron complexes and their luminance was found to be in the order of 2400 cd m?2, for single layer devices, increasing to 4400 cd m?2 when a hole‐transporting layer is used. 相似文献
90.
The stereoselective reaction of 4-oxoazetidine-2-carbaldehydes and their corresponding imines with cyanide-based reagents give β-lactam α-aminonitriles, which are chameleonic building blocks for the controlled synthesis of a variety of new compounds including functionalized γ-lactams, succinimide derivatives, and diamino-lactams derivatives in optically pure form. 相似文献