Solid-supported Hantzsch—Biginelli reaction for syntheses of pyrimidine derivatives

The microwave-assisted dry media technology was utilized for the synthesis of some novel derivatives in the Hantzsch—Biginelli reaction. In this eco-friendly approach, the usage of organic solvents and hazardous reagents resulting in corrossion of materials was minimized, giving high yields of products within a short reaction time.     

Reactions of dimethyl acetylenedicarboxylate—VI : Reaction with aldehyde and ketone phenylhydrazones

Benzaldehyde phenylhydrazone with dimethyl acetylenedicarboxylate gives dimethyl 1,3-diphenylpyrazoline-4,5-dicarboxylate, dimethyl 1,3-diphenylpyrazole-4,5-dicarboxylate and trimethyl 1-phenylpyrazole-3,4,5-tricarboxylate; p-chlorobenzaldehyde phenylhydrazone gives trimethyl 1-phenyl-3,4,5-tricarboxylate and 1,2-(bis-phenylazo)-1,2-di-p-chlorophenylethane. Under similar conditions, p-tolualdehyde phenylhydrazone gives only trimethyl 1-phenylpyrazole-3,4,5- tricarboxylate. Acetophenone phenylhydrazone with dimethyl acetylenedicarboxylate gives dimethyl 1,3-diphenylpyrazole-4,5-dicarboxylate. Benzophenone phenylhydrazone, on the other hand, gives a mixture of dimethyl 1,3-diphenylpyrazoline-4,5-dicarboxylate and dimethyl 1,3-diphenylpyrazole-4,5- dicarboxylate. Benzyl methyl ketone and dimethyl acetylenedicarboxylate gives an enamine maleate, which is the Michael addition product.     

Electron spin-spin contact interaction in many-electron atoms

A general formulation has been developed for the evaluation of the total electron spin-spin contact interaction in many-electron atoms, including both the intra- and inter-shell contributions. Calculations have been carried out, using existing analytical Hartree-Fock functions, for the positive ions, neutral systems, and negative ions for all the atoms from He to Kr.

---

Zusammenfassung Es wird ein allgemeiner Formalismus zur Berechnung der gesamten Elektronen-Spin-Spin-Kontakt-Wechselwirkung in Vielelektronen-Atomen angegeben, der sowohl die Anteile der Wechselwirkung innerhalb einer Schale als auch zwischen einzelnen Schalen berücksichtigt. Berechnungen wurden unter Benutzung vorhandener analytischer Hartree-Fock-Funktionen für die positiven Ionen, die neutralen Systeme und die negativen Ionen aller Atome von He bis Kr durchgeführt.

---

---

This work has been supported in part by the National Research Council of Canada.     

Kinetik der Entladung von Zn2+ und Ni2+ an der Quecksilbertropfelektrode in einem Thiomalatmedium

Zusammenfassung Wir untersuchten auf polarographischem Wege die Kinetik der Entladung von Zn²⁺ und Ni²⁺ an der Quecksilbertropfelektrode in einem Thiomalatmedium konstanter Ionenstärke (=0,5). Wir stellten fest, daß die Reduktion von Zn²⁺ und Ni²⁺ irreversibel verläuft und berechneten daher die kinetischen Parameter (Übertragungskoeffizient , Geschwindigkeitskonstante der HinreaktionK _f,h ^o ) nach dem theoretischen Verfahren vonKoutecky in der vonMeites undIsrael erweiterten Form.

---

Kinetics of discharge of Zn²⁺ and Ni²⁺ at the D.M.E. in thiomalate media

Kinetics of discharge of Zn²⁺ and Ni²⁺ have been studied polarographically in thiomalate media of constant ionic strength (=0.5) at the dropping mercury electrode. The reduction of both Zn²⁺ and Ni²⁺ was found to be irreversible. Hence, the kinetic parameters (transfer coefficient , and forward rate constantK _j,h ^o ) have been calculated byKoutecky's theoretical treatment as extended byMeites andIsrael.

---

---

Mit 2 Abbildungen     

Some remarks on the use of rational functions as variational functions

When a Padé-type function is used as a trial function, it is necessary to investigate the location of singularities and the zeros of the optimized function. It is shown that an unacceptable wave function can sometimes yield numerically acceptable values because of the nature of the integration procedure. It is also shown that it is possible to remove the undesirable features of a lower order form by invoking the next approximation.     

Evaluation of thermal diffusion factor and diffusion coefficient from measurements on a trennschaukel

Measurements have been taken on a glass trennschaukel of eight tubes for the Ar-He system as a function of composition and with its hot and cold bulbs at 100°c and 0°c. For each mixture, several speeds for the mechanical push-pull motion of the gas which cover a wide enough range were tried. The results have been interpreted to determine the thermal diffusion factor α _T, in conventional fashion as well as on the basis of a theory characterizing the low speed operation, developed here. Four such different possibilities of α _t evaluation are discussed and values compared with the traditional ones obtained from the convection-free two-bulb apparatus. Lastly we discuss also in brief the prospect of estimating the diffusion coefficient as an important byproduct from measurements on trennschaukel runs.     

THE ESTIMATION OF PRIOR FROM FISHER INFORMATION

ＴＨＥＥＳＴＩＭＡＴＩＯＮＯＦＰＲＩＯＲＦＲＯＭＦＩＳＨＥＲＩＮＦＯＲＭＡＴＩＯＮ￥ＬＩＹＵＡＮＺＨＡＮＧ；Ｋ．Ｍ．ＬＡＬＳＡＸＥＮＡＡＮＤＱＩＡＮＧＷＥＮＪＩＵＡｂｓｔｒａｃｔ：ＩｎＢａｙｅｓｉａｎａｎａｌｙｓｉｓ，ｔｈｅｍａｘｉｍｕｍｅｎｔｒｏｐ...     

Spontaneous translation of nanodroplet over a heterogeneous surface due to thermal cycles: role of solid–liquid interfacial fluctuations

ABSTRACT

We study the molecular-scale features of the solid surface that result in the spontaneous motion of a nanodroplet due to the periodic variation of temperature. We first employ a thermodynamic model to predict the variation of solid–fluid interfacial properties that can result in the above motion. The model identifies a composite (surface couple) made of two surfaces that are characterised by a large difference between the entropic parts of the solid–liquid interfacial free energies. In order to understand the molecular-scale features of the two surfaces that may form a surface couple, we performed grand canonical Monte Carlo simulations of Lennard Jones fluid and crystalline surfaces made of Lennard Jones-like atoms. We then used the cumulant expansions of the perturbation formulas to divide the interfacial entropy into two parts: The one that is directly affected by the solid–fluid attraction (direct part), and the other (indirect part) that is indirectly affected by the solid–fluid attraction via the alteration of interfacial fluctuations. Our results indicate that two surfaces form a surface couple if the differences between their chemical natures lead to large differences in the indirect part of the interfacial entropy, while the direct part remains relatively unaffected.     

Tracks of 18·56 MeV/u 40Ar ions in Lexan polycarbonate detector

Latent damage tracks of energetic⁴⁰Ar ions (18·56 MeV/u) have been recorded in Lexan polycarbonate detector. Bulk and track-etch parameters are evaluated under successive chemical etching. Our results show a linear correlation between the measured track-etch rate along the track and the corresponding total energy-loss rate and predict a threshold value of 5·0 MeV mg⁻¹ cm² for track registration. Maximum etchable track lengths of⁴⁰Ar ions as a function of energies have also been measured and compared with three different sets of theoretical ranges.     

Structural phase transitions of the Si(100) surface

A Monte Carlo study of the structural phase transitions on the Si(100) surface for both the “(2×1)” and “c(2×2)” reconstruction families is carried out using the asymmetric dimer model. A second order phase transition is observed at about 250 K from a p(2×2) (layered antiferromagnetic) to a disordered (paramagnetic) state in the “2×1” family. A similar transition is observed about 800 K from a c(2×2) (ferromagnetic) to a disordered state in the “c(2×2)” family. These results are in agreement with real-space renormalization group results. The variation of the specific heat, susceptability and the absolute value of the order parameter as a function of temperature is obtained in the range 200 to 300 K for the “2×1” family and 750 to 850 K for the “c(2×2)” family. Also, the order parameter correlation function is computed for ten different temperatures in the above ranges.