1,2-fused pyrimidines. V. Synthesis of 1-alkyl or phenyl-2H-dipyrido-[1,2-a:2′,3′-d]pyrimidine-2,5(1H)-diones

The reaction of 2-[(N-acyl, N-alkyl or phenyl)amino]-4H-pyrido[1,2-a]pyrimidin-4-ones 8a-g with the N,N-dimethylformamide/phosphorus oxychloride Vilsmeier reagent 1 (95°, 90 minutes) afforded 1-alkyl or phenyl-2H-dipyrido[1,2-a:2′,3′-d]pyrimidine-2,5(1H)^?diones, 3-alkyl substituted or not, 10a-g . The starting compounds 8 were prepared by treating 2-amino-4H-pyrido[1,2-a]pyrimidin-4-ones N-alkyl substituted 7a,b or N-phenyl substituted 4 with excess anhydrides (130°, 7 hours) when the 2-(alkylamino) derivatives 7 were used in the reaction, compounds 8 were obtained along with very small amounts of 3-acyl-2-(alkylamino)-4H-pyrido[1,2-a]pyrimidin-4-ones 9 .     

Un teorema di unicità per una equazione iperbolica,non lineare

We prove the uniqueness of weak solutions of initial boundary value problems Each functiona _i is required to be sufficiently smooth and must satisfy the following conditions: \(e) \sum\limits_1^n {ij} \partial _{\eta _j \eta _h }^2 a_i (x, \ldots , \eta 1, \ldots , \eta _n )\xi _i \xi _j \leqslant 0, h = 1, \ldots , n,\) for some positive constantsK ₀, α, some non negative constantsK _i , some positive functionsH(t)∈L ¹(0,T) and for all ξ≡(ξ _i ), η≡(η _i )∈R ⁿ      

Positive\partial \bar \partial - closed currents and non-Kähler geometrycurrents and non-Kähler geometry

In this paper some new results on positive \(\partial \bar \partial - closed\) currents are applied to modifications \(f:\bar M \to M\) . The main result in this topic is that every smooth proper modification of a compact Kähler manifoldM is balanced. Moreover, under suitable hypotheses on the map, the Kähler degrees of \(\bar M\) corresponds to homological properties of the exceptional set of the modification. More examples ofp-Kähler manifolds are discussed in the last section of the paper.     

X-ray spectroscopic characterization of Cu2+-phenanthroline complexes intercalated in α-zirconium phosphate

X-ray photoelectron spectroscopy provides evidence that when [Cu(phen)₂]²⁺(phen = 1,10-phenanthroline) is diffused between the layers of -zirconium phosphate, the complex species does not remain intact after intercalation, but some Cu-N bonds are broken, replaced with Cu-O bonds and the released nitrogen atoms can now interact with the PO₃-OH groups of the host. XPS also provides evidence for coordination of the Cu²⁺ ions when they are diffused by ion exchange in the phenanthroline--zirconium phosphate intercalation compound. Although Cu²⁺ and phen are in a 1 : 1 molar ratio in the interlayer region of the host, so that a 1 : 1 coordination could be expected between the two species, the characteristic peaks of the uncoordinated phenanthroline, even though at a low intensity, are still present. The differences between the two Cu(II)-intercalation compounds are discussed.     

Endogenous growth of the population of reverse micelles

The coupling reaction between cetylbromide (CB) and trimethylamine (TMA) to yield the surfactant cetyltrimethylammonium bromide (CTAB) is studied in the system chloroform/isooctane (2/1,v/v)/water in which CTAB forms reverse micelles. This system affords an endogenous micelle population growth, i.e., an increase of the concentration of the micelles due to appearance of the surfactant in situ. The reaction is studied in the presence of preexisting CTAB reverse micelles. The rate of CTAB formation is measured by NMR spectroscopy, and the endogenous micelle population growth is directly monitored by time-resolved fluorescence quenching analysis. Under our experimental conditions, a 100% yield of the chemical reaction brings about a fourfold increase in the population of the reverse micelles. Since the water concentration is constant during chemical reaction, the newly formed water pools are formed at the expense of the initial ones, which brings about a decrease of the average water pool radius during micellar growth. The implication of the endogenous micelle population growth as a model for biological systems is briefly discussed.     

The Chemistry of Coumarin Derivatives. Part 5. Unusual course of the reaction of 4-hydroxycoumarin and aliphatic aldehydes

The reaction of 4-hydroxycoumarin and certain aliphatic aldehydes affords 1:1 or complex 2:2 adducts besides (or in place) of the expected 2:1 bis(coumarin) adducts. Reaction with heptanal, cyclohexanecarbaldehyde, and pivalaldehyde are reported as representative. The structure of the reaction products was established by spectroscopical techniques, including X-ray analysis, and their formation was mechanistically rationalized. Some of the 1:1 adducts are synthetically useful for the preparation of 3-alkyl-4-hydroxycoumarins.     

Alignment of molecules in pulsed resonant laser fields

We investigate by numerical simulations the dynamics of alignment of linear molecules in resonant pulsed laser fields and its dependence on pulse length, field strength, and molecular parameters. We propose an analytical short-time approximation for the time-dependent wave packets. We provide a theoretical basis for the occurrence of saturation in the rotational pumping. We present a formula to predict the time at which the maximum alignment occurs. We discuss the magnitude of the laser-induced alignment and we relate it to a theoretical upper limit.     

The ring-opening reaction of chromenes: a photochemical mode-dependent transformation

The efficiency of the photochemical ring-opening of chromenes (or benzopyrans) depends on the vibronic transition selected by the chosen excitation wavelength. In the present work, ab initio CASPT2//CASSCF calculations are used to determine the excited-state ring-opening reaction coordinate for 2H-chromene (C) and 2,2-diethyl-2H-chromene (DEC) and provide an explanation for such an unusual mode-dependent behavior. It is shown that excited-state relaxation and decay occur via a multimodal and barrierless (or nearly barrierless) reaction coordinate. In particular, the relaxation out of the Franck-Condon involves a combination of in-plane skeletal stretching and out-of-plane modes, while the second part of the reaction coordinate is dominated exclusively by a different out-of-plane mode. Population of this last mode is shown to be preparatory with respect to both C-O bond breaking and decay via an S(1)/S(0) conical intersection. The observed mode-dependent ring-opening efficiency is explained by showing that the vibrational mode corresponding to the most efficient vibronic transition has the largest projection onto the out-of-plane mode of the reaction coordinate. To support the computationally derived mechanism, we provide experimental evidence that the photochemical ring-opening reaction of 2,2-dimethyl-7,8-benzo(2H)chromene, that similarly to DEC exhibits a mode-dependent photoreaction, has a low ( approximately 1 kcal mol(-1)) activation energy barrier.     

Liquid—liquid extraction and determination of uranium(IV) with 2,6-diacetylpyridine bis(benzoylhydrazone)

2,6-Diacetylpyridine bis(benzoylhydrazone) (H₂DPBH) is proposed as a ligand for the extraction of uranium(VI). Complete extraction from aqueous solutions into dichloromethane is achieved with a ligand/metal mole ratio of < for 10^?5?10^?4 M uranyl ion. Potentiometric measurements indicate that the extracted species is UO₂ (DPBH). Uranium can be determined in the extract by spectrophotometric measurements at 420 nm and by differentail pulse polarography (E_p = ?0.67 V) with tetraethylammonium bromide as supporting electrolyte. For both methods, the detection limit is about 2 × 10^?6 M in the extract.     

On elliptic equations with an axial symmetry

Sunto Si considera l'equazione (*) au_xx+2bu_xy+cu_yy+(d/y)u_y=f dove a, b, c, d L, d > 0, f L². Supponendo che (*) sia uniformemente eliittica e che l'oscillazione del quoziente d/a verifichi una resirizione vicino all'asse della x, si provano stime a priori e un teorema di esistenza per soluzioni W^2,2 di un problema di Dirichlet relativo all'equazione (*).

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Work supported by the Istituto di Analisi Globale e Applicazioni.