Asymmetric,Three‐Component,One‐Pot Synthesis of Spiropyrazolones and 2,5‐Chromenediones from Aldol Condensation/NHC‐Catalyzed Annulation Reactions

A novel one‐pot, three‐component diastereo‐ and enantioselective synthesis of spiropyrazolones has been developed involving the aldol condensation of an enal to generate α,β‐unsaturated pyrazolones, which react with a second equivalent of enal through an N‐heterocyclic carbene (NHC)‐catalyzed [3+2] annulation. The desired spirocyclopentane pyrazolones are obtained in moderate to good yields and good to excellent stereoselectivities. Alternatively, starting from cyclic 1,3‐diketones, 2,5‐chromenediones are available through [2+4] annulation.     

Complexation of small molecules by open-ended resorcarene hosts

[structure: see text] Sterically hindered tetraaminomethylated resorcarenes form inclusion complexes in CDCl(3) with acetonitrile and acetaldehyde, which are kinetically stable on the NMR time scale at 233 K.     

Reheating as a surface effect

We describe a new mechanism for reheating the Universe through evaporation of a surface charge of a fragmented inflaton condensate. We show that for a range of Yukawa coupling of the inflaton to the matter sector evaporation gives rise to a much smaller reheat temperature compared to the standard perturbative decay. As a consequence, reheating through a surface effect could solve the gravitino and moduli overproduction problem in inflationary models without fine tuning the Yukawa sector.     

Non-parametric Estimation for the M/G/∞ Queue

Given an M/G/ queue with input rate and service-time distribution G, we consider the problem of estimating and G from data on the queue-length process Q = (Q_t). Our motivation is to study departures of G from exponentiality, following recent work of Bingham and Dunham (1997, Ann. Inst. Statist. Math., 49, 667–679).     

A smog chamber and modeling study of the gas phase NOx–air photooxidation of toluene and the cresols

An experimental and modeling study of irradiated toluene–NO_x–air, toluene–benzaldehyde–NO_x–air, and cresol–NO_x–air mixtures at part-per-million concentrations has been carried out. These mixtures were irradiated at 303 ± 1 K in a 5800-liter Teflon-lined, evacuable environmental chamber, with temperature, humidity, light intensity, spectral distribution, and the concentrations of O₃, NO, NO₂, toluene, PAN, formaldehyde, benzaldehyde, o-cresol, m-nitrotoluene, and methyl nitrate beingmonitored as a function of time. For the toluene and toluene–benzaldehyde–NO_x–air runs a variety of initial reactant concentrations were investigated. Cresol–NO_x–air runs were observed to be much less reactive in terms of O₃ formation and NO to NO₂ conversion rates than toluene–NO_x–air runs, with the relative reactivity of the cresol isomers being in the order meta » ortho > para. The addition of benzaldehyde to toluene–NO_x–air mixtures decreased the reactivity, in agreement with previous studies. Alternative mechanistic pathways for the NO_x photooxidations of aromaticsystems in general are discussed, and the effects of varying these mechanistic alternatives on the model predictions for the toluene and o-cresol–NO_x–air systems are examined. Fits of the calculations to most of the experimental concentration–time profiles could be obtained to within the experimental uncertainty for two of the mechanistic options considered. In both cases it is assumed that (1) O₂ adds to the OH–toluene adduct ～75% of the time forming, after a further addition of O₂, a C₇ bicyclic peroxy radical, and (2) this C₇ bicyclic peroxy radical reacts with NO ～75% of the time to ultimately form α-dicarbonyls and conjugated γ-dicarbonyls (e.g., methylglyoxal + 2-butene-1,4-dial) and ～25% of the time to form organic nitrates. The major uncertainties in the mechanisms concern (1) the structure of the bicyclicperoxy intermediate, and (2) the γ-dicarbonyl photooxidation mechanism. Good fits to the o-cresol concentration–time profiles in the toluene–NO_x runs are obtained if it is assumed that o7-cresol reacts rapidly with NO₃ radicals. However, it is observed that the model underpredicts nitrotoluene yields by a factor of ～10, but this is in any case a minor product. It is concluded that further experimental work will be required toadequately validate the assumptions incorporated in the aromatic photooxidation mechanisms presented here.     

List of subject

We report the high resolution emission (S₁ → S₀, T₁ → S₀) and laser single site singlet excitation (S₁ ← S₀) spectra for the various insertion sites of coronene in n-heptane cooled to 1.5 K. The observation of site splitting of doubly degenerate vibrations and weak electric dipole forbidden 0, 0 bands in the S₁ → S₀ and T₁ → S₀ spectra indicates that the ground state, the first excited singlet and lowest triplet states are all distorted. In these spectra, the intensity distribution of the various sites in the 0, 0 bands suggests that the distortion is different from site to site but similar in S₀, S₁ and T₁. Identical ordering of the sites in S₁ S₀ and S₁ S₀ spectra as well as the observation of weak shifts in the vibrational frequencies in the two states implies the absence of strong pseudo Jahn-Teller forces in the first excited singlet state. We propose, further, that this is also true for the triplet state. This conclusion is supported by the similarity in zero-field splitting parameters of coronene and deuterated coronene. Taken together, these results indicate strongly that the distortion of coronene in n-heptane is primarily crystal field induced and is not greatly changed upon excitation of the molecule to its lowest excited states.     

Identification of mononitropyrenes and mononitrofluoranthenes in air particulate matter via fused silica gas,chromatography combined with negative ion atmospheric pressure ionization mass spectrometry

This paper describes the use of high resolution capillary gas chromatography combined with negative ion atmospheric pressure ionization mass spectrometry (NIAPIMS) for the analysis of an air particulate extract for mononitropyrenes and mononitrofluoranthenes, some of which are powerful bacterial mutagens. The results are compared to those obtained by the electron impact mass spectrometric analysis of the same sample In addition, the NIAPIMS method confirmed the identification of 4-nitropyrene in the ambient air sample.     

Anion–π Interactions in Salts with Polyhalide Anions: Trapping of I42−

The directionality of interaction of electron‐deficient π systems with spherical anions (e.g,. halides) can be controlled by secondary effects like NH or CH hydrogen bonding. In this study a series of pentafluorophenyl‐substituted salts with polyhalide anions is investigated. The compounds are obtained by aerobic oxidation of the corresponding halide upon crystallization. Solid‐state structures reveal that in bromide 2 , directing NH–anion interactions position the bromide ion in an η¹‐type fashion over but not in the center of the aromatic ring. The same directing forces are effective in corresponding tribromide salt 3 . In the crystal, the bromide ion is paneled by four electron‐deficient aromatic ring systems. In addition, compounds 4 and 6 , which have triiodide and the rare tetraiodide dianion as anions, are described. Computational studies reveal that the latter is highly unstable. In the present case it is stabilized by the crystal lattice, for example, by interaction with electron‐deficient π systems.     

Non-centrosymmetric tetrameric assemblies of tetramethylammonium halides with uranyl salophen complexes in the solid state

Ditopic salophen-UO(2) receptors 1-4 and 7 co-crystallize with tetramethylammonium (TMA) chloride and fluoride salts producing good quality crystals amenable for X-ray diffraction characterization. The arrangement of the receptor and salt units in the crystal lattice is such that tetrameric ball-shaped assemblies are formed, where an inner cluster of four TMA cations are surrounded by an outer shell of four UO(2)-bound anions. These elaborate architectures, which occur in all cases, regardless of a certain degree of structural modification on the receptors, lead to lattices that belong to non-centrosymmetric (NCS) space groups. Interestingly, the tetragonal symmetry of the tetrameric ball-shaped assemblies is either retained (I4?) or lost (R3c and I4?3d) at the lattice level, without compromising the NCS nature of the crystal lattices. The principal X-ray investigation on TMAX (X = Cl/F) co-crystals, that is, 1-(TMA)Cl, 2-(TMA)Cl, 3-(TMA)Cl, 4-(TMA)Cl, 7-(TMA)Cl, and 7-(TMA)F, is accompanied by NMR and electrospray ionization (ESI) mass spectrometry studies to gather additional insight on the modality of formation of the solid state structures observed. The important role of cation-π interactions in the receptor-salt recognition process is renewed and strengthened by comparison with NMR titration data with a novel reference compound, the salophen-UO(2) complex 8. Given the importance of NCS and polar crystalline solids in the development of functional materials, this study shows that this property can be introduced into elaborate host-guest systems, as those which assemble in the architectures described here, thus expanding its field of applicability.