Synthesis of γ- dihydropyrones and β- dihydrofuranones on the basis of acetylenic γ- and δ-keto alcohols and acetals of γ- and δ-formyl alcohols

Acetylenic - and -keto alcohols and acetals of acetylenic - and -keto alcohols and acetals of acetylenic - and -formyl alcohols undergo cyclization to -dihydropyrones and -dihydrofuranones under the influence of acids.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 11, pp. 1471–1473, November, 1976.     

Zur gruppentheoretischen Bestimmung der Atomzustände in Ligandenfeldern

Zusammenfassung Es wird vorgeschlagen, die Bezeichnungen weak-field-Methode bzw. strong-field-Methode durch (L)-Methode bzw. ()-Methode zu ersetzen.Nach einer kurzen Einführung in die ()-Methode wird mit den Mitteln der Gruppen-und Darstellungstheorie eine Formel abgeleitet, mit deren Hilfe man schnell Rasse und Multiplizität der Terme eines Komplexions in der ()-Methode angeben kann. Einige Spezialfälle dieser Formel und die systematische Bestimmung der ()-Funktionen werden erörtert.

---

It is suggested that the misleading designations weak field method and strong field method be replaced by (L) method and () method, respectively.Following a brief introduction to the () method an equation is derived by group theoretical means which leads to rapid classification of the () terms. Several special cases and short cuts are discussed as well as the systematic determination of the () functions.

---

Résumé Le remplacement des termes «méthode du champ faible» et «méthode du champ fort» par «méthode (L)» et «méthode ()» est proposé.Après une introduction dans la méthode () une formule est dérivée à l'aide de la théorie des groupes et des représentations, qui donne la représentation irréductible et la multiplicité des termes d'un ion complexe dans le cadre de la méthode (). Quelques cas spéciaux de cette formule et la détermination systématique des fonctions (/gG) sont discutés.

---

---

Ich danke Herrn Professor Dr. H. Hartmann für den Hinweis auf das vorliegende Problem und der Deutsehen Forschungsgemeinschaft für ein Stipendium.     

Fast non-destructive determination of silicon in coal by means of /n,n′ γ/ and /n, γ/ processes

The possibilities were evaluated of nondestructive determination of silicon content in large-scale samples of coal /about 20–50 kg/, based on the spectrometry of prompt -radiation from processes /n, n /, E=1779 keV and /n, /, E=3539 keV and 4935 keV. The neutron sources were either²⁴¹Am–Be or²⁵²Cf located additionally in D₂O moderator. A Ge/Li/ detector was used for -radiation detection. In exposure times of up to 2 h, the detection limits of 1.3% and 0.9% and accuracies of silicon determination of 0.66% and 0.40% have been achieved in case of /n, / and /n, n / processes, respectively.     

Fluorescent Molecular Sensing System Based on Tri-Pyrenes-Labeled γ-Cyclodextrin at the Hetero Rim

Fluorescent active host labeled at the upper and lower rims of -cyclodextrin, namely, mono-3^A-deoxy-3^A-pyrenebutylamido-6^X,Y-O-bis-pyrenebutylate-mono-altro--cyclodextrin (-3) has been synthesized as a chemosensor for steroidal guests using fluorescence spectra change upon a guest addition. The -3 shows monomer and excimer fluorescence, which results in an increase of the intensity of monomer and decrease of excimer fluorescence with a host–guest binding in the cyclodextrin cavity. The extent of monomer and excimer fluorescence variations of -3 was used as an indication for the sensing ability for the guests examined. The guest-induced fluorescence changes were measured for 10^–7 M solutions of -3. The sensing parameters (I_ex/I⁰_ex and I_mon/I⁰_mono) were used to describe the sensing ability of -3. The values of I_ex/I⁰_ex describe that -3 shows less selectivity for guests than that of mono-3^A-deoxy-3^A-pyrenebutylamido-6^X-O-mono-pyrenebutylate-mono-altro--cyclodextrin (-2), and the values of I_mon/I⁰_mono show that -3 shows higher sensitivity and selectivity than that of -2.     

Spin conversion of positronium in paramagnetic solutions studied by age-momentum-correlation method

Correlated measurement of the lifetime and of the lineshape of the 511 keV annihilation radiation of positrons (age-momentum correlation, AMOC) has become a powerful tool for investigating reactions of positron or positronium in condensed matter as a function of time. The beam-based ⁺ AMOC method installed at the Stuttgart relativistic positron beam facility (E _kin ^e+ 4MeV) offers substantial advantages over the conventional E coincidence technique resulting in a fast data taking due to the unity detection efficiency of the ⁺ scintillator which provides the start signal for the lifetime measurement. In this paper the application of AMOC to positronium chemistry is illustrated by the study of spin conversion of positronium in the system methanol/HTEMPO as a function of HTEMPO (4-hydroxy-2,2,6,6-tetramethylpiperidine-1-oxyl, a paramagnetic solute) concentration. The same technique can be applied to other systems and other reactions in positronium chemistry, e. g., oxidation or complex formation.     

TLC technique for the detection and determination of gamma- BHC in biological material

Summary Five isomers present in technical benzene hexachloride were successfully separated by TLC on silica-gel G impregnated with silver nitrate solution. The -isomer was identified by running a control sample of -BHC. Measurement of the spot area was found suitable for the estimation of 5–20g of-BHC, and was applied to analysis of autopsy tissues. The limit of identification is 0.1g.

---

Zusammenfassung Auf mit Silbernitratlösung imprägniertem Kieselgel G konnten dünn-schichtchromatographisch fünf Isomere aus technischem Hexachlorbenzol erfolgreich getrennt werden. Das-Isomere wurde mit Hilfe einer Vergleichsprobe identifiziert. Die Planimetrie der Flecken eignet sich zur Schätzung von 5–20 g-Hexachlorbenzol. Die Methode wurde zur Untersuchung von Autopsieproben angewendet. Die Nachweisgrenze beträgt 0,1g.

     

A New Gamma-Ray Spectrum Catalog for PGAA

A major obstacle to the use of the prompt gamma activation analysis (PGAA) method has so far been the lack of a suitable library. Therefore, new measurements have been performed at the PGAA facility at Budapest Research Reactor (BRR) in order to create a prompt -ray catalog for qualitative and quantitative analysis. Prompt -ray energies and associated k ₀-factors have been determined by internal standardization. The resulting catalog contains prompt -ray data from neutron capture and other reactions such as (n,), and decay -ray data from short-lived reaction products. Data have been measured for nearly all stable elements, from hydrogen to uranium. Generally, data for several isotopes are given, to enable isotopic analysis as well.     

Synthesis of two regiospecific isomers of monotosyl-γ-cyclodextrin

Tosylation of -cyclodextrin in an aqueous alkaline solution gave two regiospecific isomers (2-monotosyl--cyclodextrin(1) and 6-monotosyl--cyclodextrin(2)), that could recognize and catalyze small sized guest molecules; 2-monotosyl--CD recognized small sized guest molecules more effectively than did 6-monotosyl--CD.     

Interaction of O,O-Diethyl-β-hydroxy-γ-chloropropyl dithiophosphate and β-hydroxy-γ-chloropropyl thioacetate with bases

Conclusions O,O-Diethyl thioglycidylthiolphosphate was obtained by the action of base on O,O-diethyl-hydroxy--chloropropyl dithiophosphate. 3-Thietanyl acetate was obtained by the action of base on-hydroxy--chloropropyl thioacetate.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 1, pp. 145–147, January, 1970.     

Viscoelastic behavior of linear polyethylene and of paraffin mixtures

Summary The complex shear modulus of a linear polyethylene (Marlex 50), of which samples were either crystallized from the melt at various temperatures or precipitated from a dilute xylene solution, has been measured as a function of temperature at fixed frequencies between 10⁵ and 10^–1 c/s. The three relaxation regions, , can be distinguished, and activation energies are determined from the relaxation map. The-process shows a frequency-temperature characteristic which has been divided into three parts _I, _II, _III. Further experimental evidence for the kink model, proposed in an earlier paper (reference 4) is taken from the investigation of suitable paraffin mixtures. Measurements on six n-alkane systems, each consisting of an even n-paraffin mixed with a few percent of a paraffin with a chain longer by two C-atoms, are reported.

---

Zusammenfassung Es wurde die TemperaturabhÄngigkeit des komplexen Schubmoduls eines linearen PolyÄthylens (Marlex 50) bei festen Frequenzen zwischen 10^–1 und 10⁵ Hz untersucht, wozu die Proben entweder aus der Schmelze bei verschiedenen Temperaturen kristallisiert oder aus verdünnter Xylollösung bei 80 C gefÄllt, in Methanol ausgewaschen und gepre\t worden waren. Drei Dispersionsgebiete, , können unterschieden werden. Die/max-1/T- Charakteristik des -Relaxations-prozesses wird in drei Bereiche _I, _II, _III unterteilt. Aktivierungsenergien werden aus geradlinigen Kurvenstücken dieser Charakteristiken bestimmt.Eine erneute experimentelle Stütze für das in einer früheren Arbeit (4) vorgeschlagene Kinkenmodell stellen Messungen an 6 weiteren n-Paraffin-Mischungssystemen dar, wobei die KettenlÄngen der Mischungspartner sich jeweils um zwei CH₂-Gruppen unterscheiden.

---

---

Parts of this paper were read at the 4th International Congress on Rheology, Providence R. I., 1963.     

Synthesis of organocyclosiloxanes containing cyanoalkyl groups on the silicon atom

The cohydrolysis of-cyanoethyl- and-cyanopropylmethyldichlorosilanes with dimethyldichlorosilane has been studied and the optimum conditions ensuring the maximum yield of rings containing cyanoalhyl groups have been determined.B is(-cyanoethyl)hexamethylcyclotetrasiloxane,-cyanopropylpentamethylcyclotetrasiloxane, and bis(-cyanopropyl)hexamethylcyclotetrasiloxane have been obtained for the first time and characterized.     

Spin probe studies on high temperature (T >T g) microdynamics of polyamide 66 fibers

Summary Short-range segmental motions of the amorphous phase of polyamide 66 were studied by means of spin probe radicals. In a dry sample the relaxation in the temperature range 366–426 with an activation energy 27.6 kJ/mol was found. In a sample containing traces of water two processes, and relaxations, with activation energies 47.0 kJ/mol and 22.0 kJ/mol, respectively, were found. relaxation was dominant in the higher temperature range (410–460 K) while relaxation was active at lower temperatures (365–410 K).

---

Zusammenfassung Die inneren, lokalen Drehbewegungen in den amorphen Bereichen des Polyamid 66 wurden mit Hilfe der Paramagnersondenmethode untersucht. Wasserfreies Polyamid 66 zeigt den-Relaxations-prozeß (die Aktivierungsenergie 27.6 kJ/Mol) im Temperaturbereich von 366 K bis 426 K, wasserhaltiges Polyamid 66 zeigt zwei Prozesse,- und-Relaxationen, deren Aktivierungsenergien 47.0 kJ/Mol und 22.0 kJ/Mol sind. Die-Relaxation dominiert in dem höheren Temperaturbereich (von 410 K bis 460 K) und die-Relaxation in dem niederen Temperaturbereich (von 365 K bis 410 K).

     

Triazole derivatives as analytical reagents. Part V. Analytical studies of β-resorcylazomercaptotriazole (METRIAREZ-β) and γ-resorcylazomercaptotriazole (METRIAREZ-γ) acids

METRIAREZ- and -, two new derivatives of 5-mercapto-1,2,4-triazole with - and -resorcylic acids have been synthesized and their physicochemical and chelating properties determined. With metal ions havingp andd electrons they form water-soluble coloured chelates at L M molar ratios of 1 1 with Cu²⁺ and Pb²⁺ ( and ), Hg²⁺ and Zn²⁺ () and Cd²⁺, In³⁺ and Bi³⁺ () and 2 1 with Fe³⁺, Fe²⁺, Co²⁺ and Ni²⁺ ( and ) and Zn²⁺ (). The chelates are non-extractable by organic solvents. The stability constants of these complexes, as well as their spectrophotometric sensitivity and extinction coefficients were determined. Iron and zinc in multivitamin tablets were determined spectrophotometrically using the ligands.     

Efficiency calibration and summation effects in gamma-ray spectrometry

Precise, absolute -ray efficiences ( ) and total efficiences ( _T), have been measured at various distances from the detector, using a set of standards. The observed linear variation of and _T as well as / _T with E and provides a simple means of interpolation and extrapolation. Experimental coincidence summation effects were determined for various nuclides and compared with calculated values. The results are found to be in good agreement with each other.     

Gamma radiolysis of Methyl Red solution and reaction induced by γ-irradiated NaCl in Methyl Red

The -radiolysis of Methyl Red solution in HCl medium at pH=2 has been studied along with energy transfer reaction brought about byF and hole centers of -irradiated NaCl. The G-values for degradation of the azo dye indicator by radiolysis and -irradiated salt were determined as 9·10^–1 and 4.8·10^–3, respectively. The kinetic rate constants (k) of degradation are evaluated as 2·10^–5 rad^–1 in the case of direct radiolysis, while for the irradiated salt it is 2·10^–7 rad^–1. The extent of degradation by direct -radiolysis is 100–200 times greater as compared to that by the -irradiated salt. The same mechanism is proposed for radiolysis as well as the reaction induced by -irradiated sodium chloride.     

The conformational preferences of γ-lactam and its role in constraining peptide structure

Summary The conformational constraints imposed by -lactams in peptides have been studied using valence force field energy calculations and flexible geometry maps. It has been found that while cyclisation restrains the of the lactam, non-bonded interactions contribute to the constraints on of the lactam. The -lactam also affects the (,) of the residue after it in a peptide sequence. For an l-lactam, the ring geometry restricts to about-120°, and has two minima, the lowest energy around-140° and a higher minimum (5 kcal/mol higher) at 60°, making an l--lactam more favourably accommodated in a near extended conformation than in position 2 of a type II -turn. The energy of the +60° minimum can be lowered substantially until it is more favoured than the-140° minimum by progressive substitution of bulkier groups on the amide N of the l--lactam. The (,) maps of the residue succeeding a -lactam show subtle differences from those of standard N-methylated residues. The dependence of the constraints on the chirality of -lactams and N-substituted -lactams, in terms of the formation of secondary structures like -turns is discussed and the comparison of the theoretical conformations with experimental results is highlighted.     

Order and disorder in mixed metal linear chains: The homo and heterobimetallic EDTA (M(H2O)4OIOII)[M′(EDTA)] · 6H2O complexes (M = Mg,Mn, Co,Zn and Ni; M′ = Co,Ni, Cu and Zn)

Summary Polymetallic solid solutions of the ethylenediaminetetracetic acid (EDTA) and six divalent metal ions exist in the range: MgMnCoZnNiCu(EDTA) · 6H₂O where + + + + + =2, 01, 0,,2, 0, 1.This type of structure is characterized by the presence of two different octahedral carboxylate-bridged coordination sites forming infinite zig-zag chains. Visible and i.r. spectra and t.g.a. analysis show that there is occupational preference for the two coordination sites in the crystalline structure.Due to this preference, and also to the structural features, the heterobimetallic MM(EDTA) · 6H₂O compounds constitute a structurally new class of materials which can be described as ordered alternating-heterobimetallic polymeric coordination complexes.     

Ferrocenasymmetrie, 4. Mitt.: Die Absolutkonfiguration von (β- und γ-Phenyl-α-ketotetramethylen)-ferrocen

Zusammenfassung Ringschluß von -bzw. -Phenyl--ferrocenyl-buttersäure liefert die homoannular überbrückten Ketone (- bzw. -Phenyl--ketotetramethylen)-ferrocen (VI, VII, XIV). Die Ermittlung der Absolutkonfiguration dieser Ketone gelang durch Korrelation des Asymmetriezentrums der optisch aktiven -Phenyl--ferrocenyl-buttersäure (deren Absolutkonfiguration primär bestimmt wurde) mit der Konfiguration des planar asymmetrischen Anteils in den optisch aktiven Ketonen.Die erhaltenen Ergebnisse waren auch mit der früher für (+)-1,2-(-Ketotetramethylen)-ferrocen (I) auf unabhängigem Weg ermittelten Konfiguration in Einklang, wie durch Messung des optischen Circulardichroismus erwiesen werden konnte: die rechtsdrehenden Enantiomeren besitzen die (R), die linksdrehenden (S)-Konfiguration.

---

Ring closure of - and -phenyl--ferrocenylbutyric acid yielded the corresponding homoannularily bridged ketones, (- and -phenyl--ketotetramethylene)-ferrocene (VI, VII, XIV), respectively. The absolute configuration of these ketones could be established by correlation of the asymmetric center of the optically active -phenyl--ferrocenylbutyric acid (whose absolute configuration was determined previously) with the configuration of the planar asymmetric part in the optically active ketones.The results obtained support the configuration reported earlier for (+)-1,2-(-ketotetramethylene)-ferrocene (I) and established by an independent route. The configurations could also be supported by use of optical circular dichroism, i. e., the dextrorotatory enantiomers have the (R)-configuration, the laevorotatory the (S)-configuration.

---

---

Mit 1 Abbildung

---

Über die Verwendung des Ausdruckes Ferrocen-Chiralität (bzw. Chiralitäts-Zentrum und Planar-Chiralität) vgl., Fußnote S. 266.

---

Vgl. hierzu die Fußnote auf S. 1066

---

3. Mitt. über Ferrocenasymmetrie, zugleich 24. Mitt. über Ferrocenderivate:H. Falk undK. Schlögl, Mh. Chem.96, 266 (1965).     

Notiz zum Nachweis von Hydrazin in der Tüpfelanalyse

Zusammenfassung Bei Kontakt von Salicylaldehyddampf mit essigsaurer, acetatgepufferter Hydrazinlösung entsteht gelb fluoreszierendes Salicylaldazin. In Form einer Tüpfelreaktion lassen sich durch die Fluoreszenzreaktion 0,1 Hydrazin neben 5000 Hydroxylamin nachweisen.

---

Summary Yellow fluorescing salicylaldazine is formed when vapors of salicylaldehyde come in contact with acetic acid, acetate buffered solutions of hydrazine. In the form of a spot test, 0.1 hydrazine can be detected in the presence of 5000 hydroxylamine.

---

Résumé Par contact de la vapeur de salicylaldéhyde avec une solution d'hydrazine tamponnée avec le mélange acétate-acide acétique, il se forme une salicylaldazine donnant une fluorescence jaune. Par réaction à la touche, on peut ainsi reconnaître par fluorescence 0,1 d'hydrazine à côté de 5000 d'hydroxylamine.