Description of the shape of thermoanalytical curves

Empirical parameters were chosen for the characterization of peaks (or steps) of thermoanalytical curves. The parameters were applied in studies on the repeatability, the relationship between kinetic constants and peak shape, the effect of sample thermal resistance. Kinetic constants can be estimated on the basis of peak shape parameters. Besides, approximate criteria were formulated for experiments allowing kinetic evaluation with the neglect of the heat transport within the sample. The empirical parameters were also used in checking the suitability of DSC data for purity analysis and in detecting changes of the thermal decomposition of papers caused by ageing.Zur Beschreibung von Peaks bzw. Stufen thermoanalytischer Kurven wurden emperische Parameter ermittelt, die bei der Untersuchung der Reproduziertbarkeit, der Beziehung zwischen kinetischen Konstanten und Peakform so wie des Einflusses des thermischen Wiederstandes der Probe angewendet wurden. Kinetische Konstanten können auf der Basis von Peakformparametern geschÄtzt werden. Weiterhin wurden Kriterien für Experimente ermittelt, die eine kinetische NÄherungslösung unter VernachlÄssigung des WÄrmetransportes innerhalb der Probe ermöglichen. Die empirischen Parameter wurden au\erdem bei der Untersuchung der Eignung von DSC-daten zur Reinheitsanalyse angewendet, weiterhin zum Nachweis von alterungsbedingten Änderungen der thermischen Zerzetzung von Papier.

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The authors express their thanks to Mrs E. Tóth for her valuable technical help. The permission to reproduce Figs 2–6 and 8–10 from Analytica Chimica Acta and Thermochimica Acta (Elsevier, Amsterdam) is also acknowledged.     

Synthesis of the Deuterium Labeled Isoflavone-<Emphasis Type="Italic">O</Emphasis>-glucoside 8,3′,5′-D<Subscript>3</Subscript>-Daidzin

The regio- and stereospecific glycosylation of 8,3′,5′-trideuterodaidzein 1 with α-acetobromoglucose to provide 8,3′,5′-trideuterodaidzein-7-O-β-glucopyranoside 2 is presented.     

Preparation of diastereomeric 5,8-methanobenzoxazino[2,1–6]- and [2,3–6]-1,3-benzoxazin-4-ones by reaction of norbornane/ene-condensed dihydro-1,3-oxazines with salicyl chloride

Norbornane and norbornene-condensed dihydro-1,3-oxazines 1–6 were converted with salicyl chloride to 5,8-methanobenzoxazino[2,1–6]- and -[2,3-b]-1,3-benzoxazin-4-ones 7–12. The addition takes place to the C ? N bond: after acylation, the intermediate is stabilized through cyclization to the aryl-substituted carbon by hydrogen chloride elimination. Diastereomers containing the oxazine rings in isomeric positions could be isolated in two cases. This is the first example of the isolation of diastereomers in such a salicyl chloride reaction. In contrast with earlier findings with reactions of related systems, no addition to the C ? C bond could be observed. The steric structures of the compounds were elucidated by ir, ¹H- and ¹³C-nmr spectroscopy.     

Thermal and structural study on the lattice compound 1,4-diammoniumbutane bis(theophyllinate)

Crystalline title compound (1) prepared from aqueous solution of theophylline and 1,4-diaminobutane has been structurally and thermally characterized. Both the two-step TG decomposition curve and elemental analysis of the hexagonal crystals show that it consists of theophylline and 1,4-diaminobutane in 2:1 molar ratio. Actually, presence of one type of both theophyllinate anions and 1,4-diammoniumbutane dication have been indicated by FTIR spectroscopy. The molecular structure of lattice compound (1) has been determined by single crystal X-ray diffraction, where the hydrogen positions have been obtained from differential Fourier maps. It has confirmed that the crystal is really built up from these ionic constituents bound together with an extensive net of hydrogen bonds. The coupled TG-FTIR analysis of the evolved gases has revealed that the diamine is released as a whole molecule in the first decomposition step. Clathrate 1 and the proton migration in it might serve as a structural model of solid aminophylline whose crystal structure is still unknown.     

Analysis of organic matter from witwatersrand basin (South Africa) by OTA and Py-GC-MSPreliminary results

Oxyreactive Thermal Analysis (OTA) and pyrolysis-gas chromatography-mass spectrometry (Py-GC-MS) have been performed on highly matured, uraniferous samples. Organic matter investigated by OTA gives two exothermic peaks on DTA curves. The dominant peak appearing at temperature higher than 500°C, confirm the high maturity of the organic matter. Results of analysis by Py-GC-MS complement the OTA results. The organic matter in all of the samples shows the same general pyrolysis characteristics. The pyrograms are dominated by low molecular mass aromatic hydrocarbons. The samples differ in relative abundances of the compounds. The changes in temperature and intensity of the lower-temperature peak in OTA method and differences in relative abundances of aromatic hydrocarbons were used to investigate differences in thermal maturity of the organic matter. This revised version was published online in July 2006 with corrections to the Cover Date.     

Reversal of facial selectivity in complex Diels-Alder reactions

A complex Diels-Alder reaction between a semi-cyclic diene with allylic silyloxy substituents and a bromo enone presented an unusual diastereoselectivity: attack of the diene occured on its more hindered face, and this reversal of selectivity was shown to be induced by the presence of a bromo substituent in the dienophile.     

Stereochemical Aspects in the Asymmetric Michael Addition of Chiral Imines to Substituted Electrophilic Alkenes

The Michael-type addition of chiral imines, derived from racemic alpha-substituted cyclanones and optically active 1-phenylethylamine, to electrophilic alkenes, in neutral conditions, constitutes one of the most efficient methods for the stereocontrolled construction of quaternary carbon centers. In order to create an additional stereogenic center at the alpha- or beta-position to the quaternary one, the behavior of a variety of alpha- and beta-substituted alkenyl acceptors was examined. In general, these additions are highly regioselective, the alkylation taking place predominantly, if not exclusively, at the more substituted alpha-side of the imine function; however, in some cases (electrophilic alkenes 28 and 49), significant amounts (10-15%) of regioisomeric adducts were obtained. With the exception of methyl propiolate 52, a remarkable control of the absolute configuration of the adducts were always observed with these Michael acceptors. According to the general rule we have previously proposed, the alkylation process takes place preferentially on the less hindered pi-face of the more substituted secondary enamine, in tautomeric equilibrium with the starting imine. An excellent diastereocontrol was always obtained by using the present alpha- and beta-substituted alkenes. These stereochemical outcomes can be interpreted by invoking that the reaction proceeds through a compact approach of the reactants, the hydrogen atom at the nitrogen center of the enamine being transferred to the alpha-vinylic carbon atom of the acceptor, concertedly with the creation of the C-C bond. In this respect the "endo-approach" 58, in which the electron-withdrawing group of the acceptor faced to the nitrogen atom of the enamine (case of acceptors 10, methyl methacrylate, 24, 28, 43, 47, and 49) largely prevails over the "exo-approach" 59 (case of acceptor 38). This predominant "endo-preference" can be reasonably interpreted in terms of a cooperative effect between steric and stereoelectronic factors.     

Saturated heterocycles. 57. Synthesis of 4-substituted-9,10-dialkoxy-1,6,7,11b-tetrahydro-2H-pyrimido[6,1-a]isoquinolin-2-ones

A large number of 4-substituted-9,10-dialkoxy-1,6,7,11b-tetrahydropyrimido[6,1-a]isoquinolin-2-ones were prepared by the reaction of 1-(ethoxycarbonylmethyl)-6,7-dialkoxy-1,2,3,4-tetrahydroisoquinolines with iminoethers. Reaction of the corresponding isoquinoline-1-acetic acid derivatives with iminoethers led to the formation of N-acyl-1,2,3,4-tetrahydroisoquinolin-1-acetamides. In the hydrolysis of the prepared 4-substituted-pyrimido[6,1-a]isoquinolin-2-ones, the corresponding N-acyl-1,2,3,4-tetrahydroisoquinolin-1-acetamides were obtained. While reduction of the 4-phenyl derivative resulted in the corresponding 1,3,4,6,7,11b-hexahydropyrimidinone. The steric structures of the tetrahydro- and hexahydropyrimido[6,1-a]isoquinolines were determined by nmr spectroscopy.     

Nucleocyclitols. Synthesis of substituted purinyl-muco-inositol derivatives

Several carbocyclic nucleoside analogs possessing a 6-substituted purine linked to a mesylated muco-inositol were synthesized. The coupling of triethylamine-activated 6-chloropurine with 2,3-anhydro-l,5,6-tri-O-(methanesulfonyl)-epi-inositol gave a 6-chloro purinyl muco-inositol amenable to further synthetic transformations in the heterocyclic moiety by substitution of the chlorine atom by nitrogen nucleophiles such as methylamino, diethylamino, benzylamino, hydrazino, morpholino, hydroxylamino, piperidino, and glycyl groups.     

Thermodynamic study of the three isomers of bromo and iodobenzoic acids. Part II

Using our technique of combustion of small amount of a substance, we determined by calorimetry the standard molar enthalpy of formation in the condensed state and atT=298.15 K of the three isomers of bromo and iodobenzoic acids. Associating to these values their standard molar enthalpies of sublimation previously measured, it was possible to determine their standard molar enthalpies of formation in the gaseous state and atT=298.15 K. The experimental values of the thermodynamic properties _f H _m ^o (cr, 298.15 K), _f H _m ^o (cr, 298.15 K), _sub H _m ^o (298.15 K), and _f H _m ^o (g, 298.15 K) are given for the two series. From the experimental value of the standard molar enthalpy of atomization, it was possible to determine an enthalpy value for the C_b-Br and C_b-I bonds. The experimental and theoretical values of the resonance energy of bromo and iodobenzoic acids are compatible. The relative stability of some monosubstituted derivatives of benzoic acid studied in our laboratory is also discussed.Part I is concerned with Ref. 22 (for bromobenzoic acids) and with Ref. 23 (for iodobenzoic acids).