Synthesis of azetidin-3-ones. Structure of N-tosyl-2-ethylazetidin-3-one

A one-step synthesis of azetidin-3-ones by intramolecular cyclization of 1-diazo-3-arenesulfamoylalkan-2-ones was developed. The yield of cyclic product increases to 70% in the presence of an alkyl or benzyl substituent in the hydrocarbon chain of the diazoketone. The structure of N-tosyl-2-ethylazetidin-3-one was studied by x-ray diffraction analysis and it was shown that the four-membered ring has 15 inflection.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 4, pp. 468–473, April, 1987.     

Grain Boundary Wetting in Polycrystals: 1. Probability of Wetting of Structural Elements

A model describing the wetting of structural elements in polycrystals such as grain boundaries (faces), triple lines (edges), and quaternary nodes (vertices) is proposed. It is assumed that the only driving force during wetting is the tendency of a system to the energy minimization due to the substitution of low-energy liquid–solid interfaces for high-energy grain boundaries. In this case, the anisotropy of grain boundary energy caused by the differences in misorientation of adjacent grains is taken into account, whereas the liquid–solid interface energy is assumed to be independent of the orientation. The well-known condition of grain boundary wetting (the Gibbs–Smith condition) is extended to the triple lines and quaternary nodes by introducing parameters determined as characteristic free energy of these elements.     

Speciation of beryllium, nickel, and vanadium in soil samples from Csepel Island, Hungary

Sequential leaching methods have been used for the speciation of Be, Ni, and V in five soil samples from Csepel Island on the Danube river located near an oil-fired power plant. The concentrations of the elements of the extracts were determined by inductively coupled plasma mass spectrometry. The total efficiency (the sum of the extracted metals divided by metal fraction which is soluble in aqua regia) of the five-step method was always higher. The difference for Ni was considerable, because of the high abundance of Ni found in the moderately reducible fraction, which is absent from the three-step method. The sum of the mobile species (exchangeable, carbonatic, and easily reducible) determined by both methods, were in reasonable agreement; this was not so for the individual fractions. There were greater differences between the non-mobile fractions (moderately reducible and oxidizable), because of the presence or absence of the moderately reducible fraction. For both methods there was good correlation between the oxidizable fraction and the organic matter content of the soils.     

Use of D–T-produced fast neutrons for in vivo body composition analysis: a reference method for nutritional assessment in the elderly

Body composition has become the main outcome of many nutritional intervention studies including osteoporosis, malnutrition, obesity, AIDS, and aging. Traditional indirect body composition methods developed with healthy young adults do not apply to the elderly or diseased. Fast neutron activation (for N and P) and neutron inelastic scattering (for C and O) are used to assess in vivo elements characteristic of specific body compartments. Non-bone phosphorus for muscle is measured by the ³¹P(n,)²⁸Al reaction, and nitrogen for protein via the ¹⁴N(n,2n)¹³N fast neutron reaction. Inelastic neutron scattering is used to measure total body carbon and oxygen. Body fat is derived from carbon after correcting for contributions from protein, bone, and glycogen. Carbon-to-oxygen ratio (C/O) is used to measure the distribution of fat and lean tissue in the body and to monitor small changes of lean mass. A sealed, D–T neutron generator is used for the production of fast neutrons. Carbon and oxygen mass and their ratio are measured in vivo at a radiation exposure of less than 0.06 mSv. Gamma-ray spectra are collected using large BGO detectors and analyzed for the 4.43 MeV state of carbon and 6.13 MeV state of oxygen, simultaneously with the irradiation. P and N analysis by delayed fast neutron activation is performed by transferring the patient to a shielded room equipped with an array of NaI(Tl) detectors. A combination of measurements makes possible the assessment of the quality of fat-free mass. The neutron generator system is used to evaluate the efficacy of new treatments, to study mechanisms of lean tissue depletion with aging, and to investigate methods for preserving function and quality of life in the elderly. It is also used as a reference method for the validation of portable instruments of nutritional assessment.     

Paradigms and Paradoxes: Thoughts on the Enthalpy of Formation of Guanidine and Its Monosubstituted Derivatives

Despite their seeming simplicity, substituted guanidines have not particularly caught the attention of the thermochemical community. The current paper compares the enthalpy of formation of solid substituted guanidines with correspondingly substituted benzenes, also as solids.     

On the Synthesis of Some 2-Arylhydrazono-3-oxothieno[2,3-<Emphasis Type="Italic">b</Emphasis>]pyridines by Reaction of Nitrilimines with 2-Mercaptonicotinic Acid

Summary. Nitrilimines prepared from N-arylhydrazono chlorides reacted with 2-mercaptonicotinic acid yielding the corresponding addition products, 2-[(2-oxo-1-arylhydrazonopropan-1-yl)mercapto] nicotinic acids, which were treated with 1,1-carbonyldiimidazole in THF affording by cyclocondensation the corresponding hitherto unknown 2-arylhydrazono-3-oxothieno[2,3-b]pyridines.     

The relative influences of acidity and polarity on responsiveness of small organic molecules to analysis with negative ion electrospray ionization mass spectrometry (ESI-MS)

The purpose of the work presented here was to evaluate the influence of solution composition and analyte characteristics on responsiveness to analysis with negative ion electrospray ionization mass spectrometry. The responses of a series of structurally diverse acidic molecules were compared in various solvents. Response was generally observed to be higher in methanol than acetonitrile and response for all analytes was poorer when water was mixed with the organic solvent. A positive correlation between negative ion ESI-MS response and log P was observed when either acetonitrile or methanol was used as the electrospray solvent. This result was expected because analytes with significant nonpolar character should be particularly responsive to ESI-MS analysis due to their higher affinity for electrospray droplet surfaces. It was also predicted that highly acidic analytes would be most responsive to analysis with negative ion ESI-MS due to their tendency to form negative ions. However, for the analytes studied here, acidity was found not to have a consistent influence on ESI-MS response. Many of the highly acidic molecules were quite polar and, consequently, were poorly responsive. Furthermore, the deprotonated molecular ion was detected for a number of molecules with very high pKa values, which would not be expected to form negative ions in the bulk solution. Ultimately, these results indicate that acidity is not a conclusive parameter for prediction of the relative magnitudes of negative ion ESI-MS response among a diverse series of analytes. Analyte polarity does; however, appear to be useful for this purpose.     

Solvent dependent conformational isomerism and ligand oxidation of novel Ru(II) cyclen complexes

The synthesis of cis-[Ru(II)(cyclen)(L)(x)](n+) (cyclen = 1,4,7,10-tetraazacyclododecane and L = 2,2'-bipyridine (bpy), phenanthroline (phen) or 4-cyanopyridinium (4-NCpyH(+))) is reported. The freshly prepared complexes are stable in aprotic solvents and cyclen undergoes oxidative dehydrogenation reaction at high pH. These compounds also present solvent dependent conformational isomerization.     

A study of the tautomerism of the N-alkyl-3-methoxycarbonyl-4-piperidinones and their hydrochlorides

The positions of the equilibria of N-alkyl-3-methoxycarbonyl-4-piperidinones in the liquid state, in water, in alcohols, and in CCl₄ have been determined by IR and UV spectroscopy. It has been shown that Meyer's equation is not satisfied for them. This is due to the high steric requirements of the solvating electron pair of the nitrogen atom. On the basis of the fact that on passing from the methyl ester of cyclohexan-1-one-2-carboxylic acid to the N-alkyl-3-methoxycarbonyl-4-piperidones the position of the equilibrium in the liquid state and in CCl₄ does not shift in the direction of the enol it is deduced that the spatial requirements of the free electron pair of the nitrogen atom do not appreciably exceed the steric requirements of the hydrogen atom. The IR and UV spectra of the chlorides of the N-alkyl-3-methoxycarbonyl-4-piperidinones in the solid state and in water and in alcohols are given.     

Beitrag zur Kenntnis der Pt(II)-Verbindungen mit Acetoxim

Zusammenfassung Es wurde die thermische Zersetzung dercis-undtrans-Isomeren des [PtAox ₂Cl₂] sowie des [PtAox ₃Cl]Cl mit Hilfe derTG-undTD-Kurven im Falle des reinen Komplexes sowie im Falle einer Mischung mit Al₂O₃ (1:3) geklärt. Dietrans-Form ist stabiler als diecis-Form, die Zersetzung wird durch Al₂O₃ nicht beeinflu\t. [PtAox ₃Cl]Cl wird infolge der Erhitzung in die stabileretrans-Form [PtAox ₂Cl₂] umgewandelt und verhält sich auch weiterhin wie diese.

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A contribution to the study of the compounds of Pt(II) with acetoxime

The thermal decomposition ofcis- andtrans-[PtAox ₂Cl₂] and of [PtAox ₃Cl]Cl was studied by means ofTGA andTDA on pure substances as well as on mixtures with Al₂O₃ (1:3). Thetrans form is more stable then thecis form, the presence of Al₂O₃ has no influence on its decomposition. The [PtAox ₃Cl]Cl is transformed by heating into the more stabletrans-isomer and its further behaviour is identical with that of thetrans isomer.

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