Thermal investigations on the crystallization of sorbitol

The melting and crystallization of sorbitol were investigated with the DSC method and thermal microscopy. Sorbitol was found to have two crystalline modifications (confirmed by X-ray diffraction) with different melting points, while rapid cooling of molten sorbitol resulted in an amorphous form. The effect of inoculation on the crystallization of the melt was studied too. Powders of both crystalline modifications were used for this purpose. A new technological process for rapid crystallization of molten sorbitol has been worked out on the basis of the thermal analysis results.     

Kinetic study of copper(II) complexation with 9-ethyl-3-carbazolecarboxaldehyde-thiosemicarbazone and kinetic-spectrophotometric determination of copper(II)

The kinetics of complexation reaction of Cu(II) with 9-ethyl-3-carbazolecarboxaldehyde-thiosemicarbazone (ECCAT) has been examined spectrophotometrically. The ligand was synthesized for the first time. The complexation reaction was carried out in a DMF-water medium at 35°C. The complex has maximum absorbance at 393 nm. Kinetic and activation parameters of the complexation reaction were calculated by the Arrhenius and Eyring equations using the data obtained from investigating the effect of temperature on reaction rates under the specified conditions. We also proposed reaction rate equations. Based on the studied complexation reaction, a simple kinetic method for the spectrophotometric determination of copper(II) has been developed. The calibration graphs are linear in the concentration range 0.2–1.9 μg/mL. The species that caused interference were investigated. The text was submitted by the authors in English.     

Thermal analysis of metal complexes,III

On the basis of the thermal investigation of Mpy_nX _z mixed complexes (where M=Mn²⁺, Co²⁺, Ni²⁺, Cu²⁺, Zn²⁺, Cd²⁺; py=pyridine; or-, - and-picoline; X=Cl^–, Br^–, I^–, OCN^–, SCN^–, NO ₃ ^– , SO ₄ ^2– ; andn=2,3,4,6;z=1,2), factors influencing the stability of the metal-pyridine-N bond have been determined.On the basis of the measured magnetic susceptibilities the symmetry of the coordina tion sphere of the central atom has been established in the intermediate products formed by the thermal decomposition of cobalt(II) complexes.

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Zusammenfassung Aufgrund derivatographischer Untersuchungen von Mischkomplexen des Typs Mpy_nX_z (M=Mn²⁺, Co²⁺, Ni²⁺, Cu²⁺, Zn²⁺, Cd²⁺; py=Pyridin,, und Piccolin; X=Cl^–, Br^–, I^–, OCN^–, SCN^–, NO ₃ ^– , SO ₄ ^2– ;n=2, 3, 4, 6;z=1, 2) wurden die die StabilitÄt der Metall-Pyridin-N Bindung beeinflussenden Faktoren geprüft. Durch Messung der magnetischen SuszeptibilitÄten wurde die Symmetrie der KoordinationssphÄre des Zentralatoms des bei der thermischen Zersetzung entstehenden Kobalt(II)-komplexes ermittelt.

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Résumé On a examiné des complexes du type Mpy _n X _z (où M=Mn²⁺, Co²⁺, Ni²⁺, Cu²⁺, Zn²⁺, Cd²⁺; py=pyridine,-,- et-piccoline; X=Cl^–, Br^–, I^–, OCN^–, SCN^–, NO ₃ ^– , SO ₄ ^2– ;n=2, 3, 4, 6;z=1, 2) dans le but de déterminer les facteurs ayant une influence sur la stabilité de la liaison métal-pyridine-N. Par mesure des susceptibilités magnétiques, on a pu établir dans la cas des complexes du Co²⁺ la sphère de coordination de l'atome central pour les phases intermédiaires produites par décomposition thermique.

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_nz ( M=n²⁺, ²⁺, Ni²⁺, Cu²⁺, Zn²⁺, Cd²⁺; py= , , ; X=Cl^–, Br^–, I^–, OCN^–, SCN^–, NO₃ ^–, SO ₄ ^2– ; n=2, 3, 4, 6; z=1, 2) , --N. , (II).

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Previous paper of the series: G. Liptay, K. Burger, E. Papp Molnár, Sz. Szebeni, F. Ruff: J. Inorg. Nucl. Chem. 31 (1969) 2359.

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We are indebted to Miss é. Szabó for technical assistance.     

On distribution of molecular weight in anionic polymerizates of caprolactam

Measurement has been made of the dependence of the molecular weight distribution on the ratio of the catalytic system components and on the polymerization time for polycaprolactam obtained by anionic polymerization. A bimodal character of the curves was observed for products made using molar ratios of activator (N-benzoylcaprolactam) to initiator (sodium dihydro-bis(methoxyethoxy)aluminate) of 1:1 and 1:3, when the polymerization times were less than 1 hr. This course is explained by the influence of fast side-reactions, mainly condensations. For a ratio of 3:1 of the components of the catalytic system, smooth integral distribution curves are obtained, accounting for a very fast decrease in the strong base concentration in the initial stages of the polymerization.     

Molecular orbital studies on the conformation of GABA (γ-aminobutyric acid)

In distinction to Extended Hückel Theory which predicts as the most stable conformation of free zwitterionic GABA a totally extended form, PCILO and SCF ab initio studies show that the intrinsically preferred conformation of the isolated molecule is a highly folded one, resulting from strong interactions between the two charged ends. Computations are also carried out for hydrated GABA in the supermolecule approach allowing moreover for the flexibility of binding of some of the water molecules of the first hydration shell. They predict the coexistence in solution of a large number of conformations showing different degrees of folding (or extension), a result confirmed by recent NMR studies. This and a number of similar results show that we have to adapt our thinking on the role of conformations in pharmacological activity to this situation, which was frequently obscured by the more abundant results of X-ray crystallography yielding a single conformation.     

Addition of hydroxide to an isoelectronic series of bis-diazineplatinum(II) complex ions

Base hydrolysis of bis-bipyridylplatinum(II) occurs via a 1:1 intermediate adduct with hydroxide ion. The equilibrium constants for this 1:1 addition of hydroxide inwater to complex ions [PtL2]2+, where L=one of theisoelectronic set 2,2-bipyridyl (bpy); 2,2- bipyrazine (bpz); 3,3-bipyridazine (bpdz) and 2,2- bipyrimidine (bpym) are respectively (as log10K at 25°C): 4.23; 4.59; 3.82; 6.14. This result is rationalized in terms of addition at the 6–position of the ligand.     

Studies on stereoselective approaches to β-carboline derivatives

Transformation of β-carboline derivatives into optically active entities were studied and the de and ee values of the resulted compounds were detected. Dedicated to Professor Károly Lempert on his 80th birthday.     

Heterocyclic bioantioxidants. 2. Interaction of 3-nitro-4-substituted coumarins with mercaptans

3-Nitro-4-chlorocoumarin forms 3-nitro-4-substituted coumarins when it reacts with an equimolar quantity of benzyl mercaptan or thiosalicylic acid; with excess benzyl mercaptan, it forms 3,4-di-S-benzyl coumarin. 3-Nitro-4-methoxycoumarin under the same conditions, with an equimolar ratio of reagents, forms a mixture of monosubstituted and disubstituted products. A mechanism is proposed for these reactions.For Communication 1, see [1].Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 11, pp. 1476–1479, November, 1991.     

Branching of anionic poly(methyl methacrylate)

A viscometric determination of the degree of branching γ, of poly(methyl methacrylate) obtained by anionic polymerization proved the reaction of the growing center of poly(methyl methacrylate) with the ester group of another polymer molecule, accompanied by the formation of a trifunctional branch point. This reaction occurs if the solution polymerization of methyl methacrylate is initiated: (1) with butyllithium at ?78°C only on attaining 100% conversion and after a long time or at +20°C immediately after the polymerization has set in; (2) with lithium tert-butoxide at +20°C after a long time. The degree of branching of poly(methyl methacrylates) obtained under similar conditions in the presence of tetrahydrofuran reaches higher values than for polymers prepared in toluene. The tacticity of polymers does not affect the experimentally determined γ values.     

Stereochemical studies—76 saturated heterocycles—63 : synthesis of cis- and trans-n-methyl- and n-benzyl-4.5- and 5,6-tetramethylenetetrahydro-1,3-oxazines; an x-ray study of n-benzyl-cis-4,5-tetramethylenetetrahydro-1,-3-oxazinium- picrate

- The corresponding $\text{cis}$- and $\text{trans-N}$-methyl- and $\text{N}$-benzyl-5,6- and 4,5-tetramethylenetetrahydro-l,3-oxazines $\text{(5a,b-8a,b)}$were synthesized from $\text{cis}$- and $\text{trans-N}$-methyl and$\text{N}$-benzyl-2- aminomethyl-1-cyclohexanols $\text{1a,b,2a,b}$, from $\text{cis}$- and $\text{trans-N}$-methyl- and $\text{N}$benzyl -2-hydroxymethyl-1-cyclohexylamines$\text{(3a,b,4a,b)}$ by reaction with formaldehyde. The aminoalcohols $\text{1a,2a,3a,b}$and $\text{4a,b}$ were prepared in considerably higher yields than in earlier procedures. NMR spectroscopy showed that the $\text{cis}$ isomers of the synthesized oxazines were conformationally homogeneous in solution, and their preferred conformation (inside or outside) depended on the steric requirement of the groups attached to the anellation points, whereas a bulky C-2 substituent had no influence on the predominant conformation. The structure of $\text{N}$-benzyl-$\text{cis}$-4,5-tetramethylenetetrahydro-1,3-oxaziniumpicrate $\text{(7b)}$. determined by X-ray diffraction analysis, was in agreement with the predominant N-outside conformation of the corresponding base, established by means of NMR spectroscopy.