Catalyzed addition of acid chlorides to alkynes by unmodified nano-powder magnetite: synthesis of chlorovinyl ketones, furans, and related cyclopentenone derivatives

Inexpensive and commercially available nano-powder magnetite is an excellent catalyst for the addition of acid chlorides to internal and terminal alkynes, yielding the corresponding chlorovinyl ketones in good yields. The process has been applied to the synthesis of 5-chloro-4-arylcyclopent-2-enones, 3-aryl-1H-cyclopenta[a]naphthalen-1-ones, and (E)-3-alkylidene-2,3-dihydro-1H-cyclopenta[a]naphthalen-1-ones, just by changing the nature of the starting acid chloride or the alkyne. All tested processes elapse with an acceptable or excellent regio- and stereo-selectivity. Moreover, the use of the iridium impregnated on magnetite catalyst permits the integration of the chloroacylation process with a second dehydrochlorination–annulation process to yield, in one-pot, 1-aryl-2,4-dialkylfurans in good yields, independently of the nature of the starting reagents, and including the heteroaromatic ones.

Reduction of tobacco smoke components yield in commercial cigarette brands by addition of HUSY, NaY and Al-MCM-41 to the cigarette rod

The effect of two zeolites, HUSY, NaY and a mesoporous synthesized Al-MCM-41 material on the smoke composition of ten commercial cigarettes brands has been studied. Cigarettes were prepared by mixing the tobacco with the three powdered materials, and the smoke obtained under the ISO conditions was analyzed. Up to 32 compounds were identified and quantified in the gas fraction and 80 in the total particulate matter (TPM) condensed in the cigarettes filters and in the traps located after the mouth end of the cigarettes. Al-MCM-41 is by far the best additive, providing the highest reductions of the yield for most compounds and brands analyzed. A positive correlation was observed among the TPM and nicotine yields with the reduction obtained in nicotine, CO, and most compounds with the three additives. The amount of ashes in additive free basis increases due to the coke deposited on the solids, especially with Al-MCM-41. Nicotine is reduced with Al-MCM-41 by an average of 34.4% for the brands studied (49.5% for the brand where the major reduction was obtained and 18.5 for the brand behaving the worst). CO is reduced by an average of 18.6% (ranging from 10.3 to 35.2% in the different brands).

Solvent-dependent enantioswitching in the Michael addition of α,α-disubstituted aldehydes to maleimides organocatalyzed by mono-N-Boc-protected cyclohexa-1,2-diamines

Enantiomerically pure mono-N-Boc-protected trans-cyclohexa-1,2-diamines are used as organocatalysts for the enantioselective conjugate addition of α,α-disubstituted aldehydes to maleimides. Using a single enantiomer of the organocatalyst, both enantiomeric forms of the resulting Michael adducts bearing a new quaternary stereocenter are obtained in high yields, by only changing the reaction solvent from chloroform (up to 86% ee) to aqueous DMF (up to 84% ee).

Primary Amine–2-Aminopyrimidine Chiral Organocatalysts for the Enantioselective Conjugate Addition of Branched Aldehydes to Maleimides

Chiral primary amines containing the (R,R)- and (S,S)-trans-cyclohexane-1,2-diamine scaffold and a pyrimidin-2-yl unit are synthesized and used as general organocatalysts for the Michael reaction of α-branched aldehydes to maleimides. The reaction takes place with 10 mol% organocatalyst loading and hexanedioic acid as cocatalyst in aqueous N,N-dimethylformamide at 10 °C affording the corresponding succinimides in good yields and enantioselectivities. DFT calculations support the stereochemical results and the role played by the solvents.

Enantioselective addition of aryl ketones and acetone to nitroalkenes organocatalyzed by carbamate-monoprotected cyclohexa-1,2-diamines

Enantiomerically pure carbamate-monoprotected trans-cyclohexane-1,2-diamines are used as chiral organocatalysts for the addition of aryl ketones and acetone to nitroalkenes to give enantioenriched β-substituted γ-nitroketones. The reaction was performed in the presence of 3,4-dimethoxybenzoic acid as an additive, in chloroform as the solvent at room temperature, achieving enantioselectivities up to 96%. Theoretical calculations are used to justify the observed sense of the stereoinduction.

Solvent-Induced Reversal of Enantioselectivity in the Synthesis of Succinimides by the Addition of Aldehydes to Maleimides Catalysed by Carbamate-Monoprotected 1,2-Diamines

A simple change in the polarity of the solvent allows both enantiomers of substituted succinimides to be obtained in the enantioselective conjugate addition reaction of aldehydes, mainly α,α-disubstituted, to maleimides catalysed by chiral carbamate-monoprotected trans-cyclohexane-1,2-diamines. Using a single enantiomer of the organocatalyst, both enantiomers of the resulting Michael adducts are obtained in high yields by simply changing the reaction solvent from aqueous DMF (up to 84 % ee) to chloroform (up to 86 % ee). Theoretical calculations are used to explain this uncommon reversal of the enantioselectivity; two transition state orientations of different polarities are differently favoured in polar or nonpolar solvents.

Cabecera cuadrada renacentista con bóveda pseudo-esférica cruzada en la iglesia Santiago de Orihuela (Alicante)

Jerónimo Quijano fue uno de los ilustres arquitectos destacados del Renacimiento pleno en España. Su obra, la iglesia de Santiago en Orihuela -Alicante- posee una Capilla Mayor renacentista, de carácter funerario, de planta central y adosada a una nave gótica. Destaca su bóveda superior de 4 pares de arcos entrecruzados y revirados. Al ser dobles se reduce la superficie central de plementería y se gana en resistencia. Es de complicada geometría esférica y cuadrada a la vez: bóveda pseudo-vaída (esférica solo hasta los arcos exteriores) y plementería lateral adaptándose a la planta cuadrada. Supone la fusión de la antigüedad clásica con la tradición hispanomusulmana. Como referencia, se estudia sucintamente la Capilla Benavides en Baeza - Jaén-, obra de Andrés de Vandelvira e incluida en el tratado de arquitectura de su hijo Alonso, la cual plantea un gran espacio cuadrado cubierto por una bóveda vaída y reforzada por 4 arcos entrecruzados.

Effects of Fe addition on the mechanical and thermo-mechanical properties of SiC/FeSi2/Si composites produced via reactive infiltration

Remaining silicon in SiC-based materials produced via reactive infiltration limits their use in high-temperature applications due to the poor mechanical properties of silicon: low fracture toughness, extreme fragility and creep phenomena above 1000 °C. In this paper SiC–FeSi2 composites are fabricated by reactive infiltration of Si–Fe alloys into porous Cf/C preforms. The resulting materials are SiC/FeSi2 composites, in which remaining silicon is reduced by formation of FeSi2. For the richest Fe alloys (35 wt% Fe) a nominal residual silicon content below 1% has been observed. However this, the relatively poor mechanical properties (bending strength) measured for those resulting materials can be explained by the thermal mismatch of FeSi2 and SiC, which weakens the interface and does even generate new porosity, associated with a debonding phenomenon between the two phases.

Pseudo-organic structures from the Precambrian Bass limestone in Arizona / [by] Matthew H. Nitecki --

v.23:no.1(1971)

List of books received, Oct. 24, 1763 with 1764 addition

This document also lists volumes donated by a Mr. Bradstreet and Mr. Harris, as well as a list of "books saved [from the 1764 fire] by being borrowed" by individuals named Sewall, Parker, Cushing, Appleton, Brigden, Marsh, Cooke, Bowdoin, and Chardon.

Guérir avec l'EMDR : preuves et controverses

L'EMDR est une thérapie qui a été développée pour traiter les souvenirs traumatiques, puis proposée pour traiter une variété de troubles psychologiques. Ce texte est le premier à recenser en français les études qui ont évalué l'efficacité de cette forme de thérapie. L'efficacité de l'EMDR est d'abord démontrée à l'aide d'études de cas qui comportent des limites importantes. Les études de cas basées sur un protocole expérimental donnent des résultats plus mitigés. Les études contrôlées qui examinent l'efficacité de l'EMDR sont ensuite décrites en fonction du type de contrôle exercé et du type de trouble traité. L'EMDR est aussi efficace que la thérapie cognitivocomportementale pour traiter le trouble de stress posttraumatique, mais pas pour le traitement de la phobie spécifique ni du trouble panique. De plus, les études montrent de façon répétée que l'absence des mouvements oculaires ne modifie pas l'efficacité de l'EMDR. Une analyse des différences et des similitudes entre l'EMDR et l'approche cognitivo-comportementale est présentée. Les caractéristiques pseudo-scientifiques qui ont marquées le développement et la diffusion de l'EMDR sont aussi abordées.