General synthetic route to benz[g]isoquinolines (2-azaanthracenes)

Benzylic zinc reagents add with high regioselectivity to 1-(phenoxycarbonyl) salts derived from pyridine-3-carboxaldehyde ( 1a ) or 3-acetylpyridine ( 1b ) to yield 1-(phenoxylcarbonyl)-4-benzyl-1,4-dihydropyridine-3-carboxaldehydes 5a, 5c or ketones 5b, 5d . Aromatizations of these dihydro analogues with sulfur led to the corresponding aldehydes 6a, 6c or ketones 6b, 6d . An alternate synthesis to the aldehydic precursors involved additions of benzylic zinc reagents to 1-(phenoxycarbonyl) salts formed from methyl nicotinates which led to the corresponding methyl 1-(phenoxycarbonyl)-4-benzyl-1,4-dihydronicotinates 7a, 7b . Aromatizations of 7a, 7b led to the corresponding pyridine esters 8a, 8b which on reduction with lithium aluminum hydride yielded the corresponding carbinols 9a, 9b . Oxidation of 9a, 9b by manganese dioxide afforded aldehydes 6e, 6f . Aldehydes 6a-f were readily converted into the benz[g]isoquinolines 10a-f on heating in polyphosphoric acid.     

The synthesis and reactivity of the heptanuclear dianion [Os7(CO)20]2− including the synthesis and structural characterizations of the compounds [Os7(CO)20(AuPEt)3 2] and [Os8(CO)20(η6-C6H6]

Reduction of the heptaosmium cluster [Os₇(CO)₂₁] With [Et₄N][NH₄) gives the cluster dianion [Os₇(CO)₂₀]^2–,1, in high yield. The reaction of the dianion with [AuPR ₃Cl] (R=Et or Ph) in the presence of TlPF₆ forms [Os₇((CO)₂₀(AuPR ₃)₂] [R=Et (2a);R = Ph(2b)] in 80% yield, while the corresponding reaction with (Os(C₆H₆)(CH₃CN)₃]²⁺ gives [Os₈(CO)₂₀ ( ⁶-C₆H₆)] (3) in reasonable yield (ca. 30%). The dianion,1, and the clusters2 and3 have been fully characterized by bout spectroscopic and crystallographic methods. The crystal structure of the [Ph₄P]⁺ salt of1 shows that the metals in the anion adopt a capped octahedral geometry, with all twenty carbonyl ligands in terminal sites. The metal core geometry in2a is best described as a tricapped octahedron, and is based on the structure of the dianion1 with two adjacent octahedral faces capped by the Au atoms of the two AuPEt₃ groups. In a similar fashion, the geometry of3 is related to that of1 with the addition of an Os(C₆H₆) unit capped to a triangular face, to give a bicapped octahedral framework.     

A practical synthesis of (+/-)-alpha-isosparteine from a tetraoxobispidine core

[reaction: see text] The title alkaloid was synthesized in racemic form from 3,7-diallyl-2,4,6,8-tetraoxo-3,7-diazabicyclo[3.3.1]nonane (7) by a regioselective diallylation reaction followed by double ring-closing olefin metathesis and exhaustive reduction. Tetraoxobispidine 7 was itself prepared in three simple operations from dimethyl malonate. The entire sequence to alpha-isosparteine was conducted on a multigram scale and proceeded without recourse to chromatography.     

Light-induced coumarin cyclopentannelation

[reaction: see text] Whereas cyclopentenylcarbenes resulting from photocycloaddition of 4-alk-1-ynylcoumarins to 2,3-dimethylbut-2-ene undergo tandem cyclization to hitherto unknown tetracyclic (4-hetera)cyclopent[b,c]acenaphthylenes, the corresponding cyclopentenylnitrenes stemming from 4-cyanocoumarins and the same alkene are converted into tricyclic imines via H-abstraction.     

Ruthenium carbonyl clusters containing PMe2(nap) and derived ligands (nap = 1-naphthyl): generation of naphthalyne derivatives

Bis(dimethylphosphino)naphthalene, 1,8-(PMe₂)₂C₁₀H₆ (dmpn), reacts readily with Ru₃(CO)₁₂ or Ru₃(μ-dppm)(CO)₁₀ with replacement of one of the PMe₂ groups by H to give Ru₃(CO)_12 − n{PMe₂(nap)}_n (n = 1 2, 2 3) or Ru₃(μ-dppm)(CO)₉{PMe₂(nap)} 4; the complex Ru₃(CO)₁₀(dmpn) 1 is obtained only in small amount. Thermolysis of 2 or 4 gives Ru₃(μ-H)₂{μ₃-PMe₂(C₁₀H₅)}(μ-dppm)_n (CO)_8-2n (n = 0 5, 1 6, respectively) containing μ₃-naphthalyne groups.     

Polymerizable surfactant design for transmission electron microscopy

Polymerized liposomes and vesicles are under close scrutiny as long-lived, stable substitutes for their natural and synthetic unpolymerized counterparts. The monomer surfactant, which contains one or more polymerizable groups, is dispersed in water at the proper temperature and concentration to form the lyotropic liquid crystalline phase of interest and polymerized while in the liquid crystalline state. In addition to their applications to slow-release and site-specific drug delivery, membrane-mediated chemistry, artificial photosynthesis, etc., polymerized surfactant liposomes and vesicles hold great promise as model systems for TEM investigations of lamellar liquid crystal structure. One such model polymerizable surfactant is DBPAl, or N,N-dimethyl-N,N-bis(1,3-pentadecadienyl-carbonyloxyethyl) ammonium iodide. Polarized light microscopy and differential scanning calorimetry (DSC) confirm that DBPAI forms lamellar liquid crystalline liposomes in water. The DBPAI liposomes were polymerized while in the liquid crystalline state by ultraviolet (UV) irradiation. The DBPAI liposomes were shown to be identical in structure before and after polymerization by a combination of X-ray diffraction and freeze-fracture TEM. However, turbidity measurements showed that the polymerized DBPAI liposomes were much more stable in acetone and ethanol than the monomer DBPAI liposomes, demonstrating that the chemical nature of the surfactant in the liposome had changed. The combination of structural preservation and enhanced chemical stability makes DBPAI a natural choice for TEM thin-sections. A method of preparing DBPAI liposomes for thin-section TEM is outlined and bilayer resolution images of the DBPAI liposomes are presented. Polymerized bilayers in thin-section TEM promise the enhanced resolution required to answer many important structural questions left unresolved by freeze-fracture TEM.     

SUNSCREENS WITH BROAD-SPECTRUM ABSORPTION DECREASE THE trans TO cis PHOTOISOMERIZATION OF UROCANIC ACID IN THE HUMAN stratum corneum AFTER MULTIPLE UV LIGHT EXPOSURES

Abstract The trans to cis photoisomerization of urocanic acid (UCA) in skin is considered to play an important role in the mechanism of immunosuppression. We have investigated the effects of skin type and various sunscreens with low sun protection factor (SPF) on the UV-induced cis -UCA formation in human skin after exposure to artificial IJV light. The rate of cis -UCA formation depends little on the skin type and is reduced by topical application of sunscreens. The rate of cis -UCA formation decreases with increasing SPF and only broad-spectrum, highly protective sunscreens offer protection against the UV-induced formation of cis -UCA, which accumulates in the stratum corneum after multiple UV exposures. A theoretical approach to estimate the distribution of cis -UCA after irradiation indicates that this compound may diffuse into the deeper layers of the epidermis with D ∼ 10⁻¹⁷ m²/s, and that its elimination from the stratum corneum is mainly due to desquamation.     

A new spot test for nitro compounds

A simple, rapid, and highly sensitive method for the detection of micro amounts of nitro compounds has been developed. Nitro compounds are reduced into corresponding hydroxylamines with zinc dust and acetic acid and coupled with diazonium chloride to give hydroxytriazines which give an intense pink to violet color with diphenylamine in acetic acid medium. Quantities of 0.1 μg or less of nitro compounds can be detected in 0.25 ml of total solution by this method. The method is free from the common interference.     

On a numerical approach to Stefan-like problems

Summary This paper is devoted to the numerical analysis of a bidimensional two-phase Stefan problem. We approximate the enthalpy formulation byC ⁰ piecewise linear finite elements in space combined with a semi-implicit scheme in time. Under some restrictions related to the finite element mesh and to the timestep, we prove positivity, stability and convergence results. Various numerial tests are presented and discussed in order to show the accuracy of our scheme.This work is supported by the Fonds National Suisse pour la Recherche Scientifique.