Synthesis and stereochemical studies of 6-substituted 1H,3H,6H,7aH-3,3-dimethylimidazo-[1,5-c]thiazol-5-one-7-thiones

The reaction of (4S)-5,5-dimethyl-4-thiazolidine-carboxylic acid 1 with alkyl and aryl isothiocyanates 2 gave bicyclic thiohydantoins 3 . The (2R,4S)- and (2S,4S)-mixtures of 2-substituted 5,5-dimethyl-4-thiazolidine-carboxylic acids 4 and 8 containing two centers of chirality in the analogous reaction afforded thiohydantoins 7 and 10 , respectively, with (1R)-configuration. In some cases we managed to isolate the thioureido acid intermediates 6 and 9 or their triethylamine salts which afforded the corresponding bicycles 7 and 10 under thermal cyclization or acidification. The stereochemistry has been elucidated by high resolution ram studies, optical rotation measurements and X-ray crystallography.     

Organic Synthesis and Technetium-99m Labeling of Some Amino-Phenol Ligands

We reported the synthesis and labeling of one tetradentate and two pentadentate amino-phenol ligands with technetium-99m by the direct pertechnetate addition and by ligand exchange methods. Labeling by direct pertechnetate addition was attended by adding pertechnetate eluate to the ethanolic solution of the amino-phenol ligands at pH 9. Stannous chloride dihydrate was used as reducing agent. Exchange studies were carried out via the use of the following ^99mTc-chelates: ^99mTc-DTPA, ^99mTc-gluconate, ^99mTc-tartrate and ^99mTc-citrate complexes. Ligand exchange method was achieved by incubation the ligand solutions with ^99mTc-co-ligands complexes in 0.05M bicarbonate buffer pH 9. At this pH value the ^99mTc-co-ligands dissociated and the more stable new ^99mTc-ligands were formed with high radiochemical yield 95%. The radiochemical yield of ^99mTc-labeled amino-phenol ligands were estimated by solvent extraction, electrophoresis and HPLC methods. The produced technetium-99m amino-phenol complexes were neutral, lipophilic and stable during the period of 24 hours.     

Screening of homocysteine from newborn blood spots by high-performance liquid chromatography with coulometric array detection

Homocystinuria, due to a deficiency of cystationine-beta-synthase, refers to the rare inborn error of the metabolism of homocysteine. The identification and prompt treatment of homocystinuria during the neonatal period can prevent or greatly reduce the severity of the clinical consequences. We report a new method for homocystinuria diagnosis from dried blood spots on newborn screening cards, based on high-performance liquid chromatography with electrochemical coulometric array detection. This method shows an excellent linearity (y=10.36x+0.04; r=0.999), precision (RSDs ranged from 2.7 to 5.8%), recovery (87%) and appears to be a cost-effective approach, being simple, rapid, sensitive and cheap.     

The possibility of different time scales in the dynamics of pore imbibition

To model the imbibition of liquids into porous solids, use is often made of the Lucas-Washburn equation, which relates the distance of penetration of a liquid at a given time to the pore radius, the viscosity and surface tension of the liquid, and the effective contact angle between the liquid and the solid. In this paper, we extend previous large-scale molecular dynamics simulations to show how this tool can be used to study the details of liquid imbibition, including the impact of the contact angle on the dynamics of penetration and the evolution of the internal flow field. In particular, we show that the asymptotic behavior of the contact angle versus time for a completely wetting liquid is given by approximately t(-1/4).     

Effect of Hydration–Dehydration Processes on the Structure and Porosity of Detemplated Silica Fibers

A study was carried out on the conditions of template removal (calcination or extraction by solvents) and hydration–dehydration processes on the hexagonal structure and porosity of detemplated fibers. The hydration–dehydration cycle leads to a decrease in fiber porosity, especially in fiber detemplation by extraction with surfactant solvents such as ethanol and acetic acid.     

Thio-claisen rearrangements of some ketene derivatives

A number of 1-allylthio and 1-crotylthio 1-aminoalkenes derived from ketones and active methylene compounds has been prepared and rearranged to the corresponding thioamides (thio-Claisen rearrangement). Besides rearrangement products, small amounts of 1-alkyl-thio-N-alkyl-N-phenyl-1-aminoalkenes have also been isolated. When the ketene derivatives did possess a H-atom on nitrogen, cleavage of the formed thioamide produced phenyl isothiocyanate and substituted active methylene compounds.     

Dielektrische Relaxation Polymerer bei Temperaturen bis 1 °K

Zusammenfassung Es werden Messungen des dielektrischen Verlustes tan im Temperaturbereich von 1 bis 80 °K und bei verschiedenen Frequenzen zwischen 10 Hz und 10 kHz an einer Reihe von Polymeren mitgeteilt.Der dielektrische Verlust sinkt im allgemeinen mit Annäherung an den absoluten Nullpunkt monoton ab. Es scheint dies anzudeuten, daß immer ein dielektrischer Untergrund, beruhend auf allgemeinen thermischen Fluktuationen, existiert, der im übrigen für Polymere mit polaren Gruppen höher liegt als für unpolar gebaute. Zu tiefsten Temperaturen hin überlagert sich diesem allgemeinen Trend oft noch ein Maximum, wenngleich bei Temperaturen bis 1 °K herab zuweilen nur erst in einer Konstanz der Verlustwinkel-Werte angedeutet. Es sieht also so aus, als ob auch noch bei tiefsten Temperaturen singuläre Relaxationsmechanismen eine Rolle spielen können. In einer Reihe von Fällen findet man weitere Relaxationsprozesse zwischen 15 und 40 °K.Soweit sich Aktivierungsgrößen aus der Auftragung der Maximallage in der Temperatur mit der Frequenz nach Abtrennung des allgemeinen Untergrundes abschätzen lassen, werden diese mit sinkender Temperaturlage immer kleiner.Die dielektrischen Verluste sind in allen Fällenextrem abhängig von der Vorgeschichte der Proben und zwar insofern, daß offensichtlich Verspannungen im Material infolge von Deformationsprozessen und anderen Behandlungen zu einer erheblichen Erhöhung der Verluste führen, sowohl des Untergrundes als der singulären Mechanismen.

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Summary Investigations of dielectric loss in the temperature range 1–80 °K and with frequencies between 10 c/sec and 10 kc/sec for diverse polymers a presented. For all polymers the dielectric loss decreases in principle monotonely with the approximation of the absolute Zero-point.Thus we suppose the existence of a common dielectric background loss depending from the thermal fluctuations in the material. Moreover this background losses are higher for substances with polar groups.At the lowest temperatures in most cases there seems to appear a loss peak. For temperatures down to 1 °K often this can be only suggested from the constancy of losses. But it seems to be a quite normal fact, that for extremely deep temperatures something as a singular relaxation mechanism may exist.Further discrete mechanisms exist for the range between 15 and 40 °K. Activation energy evaluated formally from the experimental dates in the normal manner after separation of the peaks from the background becomes smaller and smaller with decreasing temperatures.In all investigated cases the dielectric losses are very sensible to prehistory of the samples. It seems, that expecially stress, by deformation and other treatments, gives rise for an increase of loss for the background as for discrete mechanisms.

     

Pyrimidines

The reaction of cyclohexanone with arylidenebisureas (e.g. benzal-bisurea) in an acid medium has given 4, 4-diaryl-2, 2-dioxo-5, 5-trimethylene-6, 6-spirobishexahydropyrimidines (II). The acid hydrolysis of IIa (aryl-C₆H₅) in the presence of 2, 4-dinitrophenylhydrazine leads to the 2, 4-dinitrophenylhydrazone of 2-hydroxy-8-oxo-4-phenyl-5, 6, 7, 8-tetrahydroquinazoline (IV). Compound IV was also obtained by the ozonization of 2-acetoxy-8-benzal-4-phenyl-5, 6, 7, 8-tetrahydroquinazoline (IX) and subsequent decomposition of the ozonide with a solution of 2, 4-dinitrophenylhydrazine. The structure of the compounds obtained was confirmed by means of their IR, UV, and PMR spectra. Corresponding 6, 6-spirobishexahydropyrimidines have also been obtained from 2-methylcyclohexanone, acetone, and methyl ethyl ketone and benzalbisurea.For part XIV, see [1].     

Structure of polymers obtained from sulfur monochloride and olefins containing sulfonium salt structures

Reactions of sulfur monochloride with diolefins lead to polymeric products which can be reduced to diepisulfides in low yield. In reactions with cyclic triolefins, polymers containing tricyclic sulfonium structures are obtained as a results of transannular additions and subsequent transannular displacements. Due to the insolubility and reactivity of these ionic structures, only incomplete structural assignements could be made, but the reactions are studied on similar cyclic structures which provide model systems.     

The vinylation of benzotriazole

The reaction of benzotriazole with acetylene under pressure in the presence of potassium hydroxide and cuprous chloride has been examined. 1-Vinylbenzotriazole was obtained in 75% yield.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 9, pp. 1289–1290, September, 1970.