Nitrogen bridgehead compounds. Part 70. Studies on quinolizine derivatives. Part 4. Ultraviolet-visible spectra and chemical properties of some quinolizine derivatives and their monocyclic tautomers

Ultraviolet-visible spectra of 4-oxo 1 and 4-imino 2 quinolizines or their monocyclic tautomers 3, 4 have been studied in neutral, acidic and basic ethanolic solution as well as in dimethyl sulfoxide and chloroform. Ring B of 4-oxo and 6-unsubstituted 4-imino compounds can be cleaved by sodium ethanolate more or less easily. Ring B of 6-methyl-4-iminoquinolizines is very unstable and they are present mainly in the monocyclic form which are partly dissociated in ethanol and dimethyl sulfoxide especially in higher dilution or in the presence of sodium ethanolate. In dilute acidic ethanol or chloroform, the dissociation is suppressed and in the latter solvent and in some cases, absorption bands can be observed due to a small amount of the 4-imino-6-methylquinolizines. In acidic solution of compounds 3B=C, 3D, 4E, 4F=G having simultaneously cyano and ethoxycarbonyl groups in 1 and 3 position, not simple reprotonation occurs but irreversible changes can be observed.     

Asymptotic behaviour of the least squares estimator of the mean of AR(1) models

The aim of the paper is to investigate the limit behaviour of the least squares estimator of the shift parameter of nearly unstable, nearly stable, and nearly explosive AR(1) models. Both zero start and stationary cases are treated. Connection with the maximum likelihood estimator of the shift parameter of continuous time AR(1) processes is also discussed.     

Gradient- and Sensitivity-Enhanced TOCSY Experiments

A pulsed field gradient version of the sensitivity-enhanced 2D TOCSY experiment is proposed which yields high-quality spectra with improved sensitivity and a minimum of two scans pert₁increment. For rapid acquisition of 1D TOCSY spectra, the 1D DPFGSE–TOCSY experiment was modified to include phase-encoded multiple-selective excitation followed by a simple spectral editing. Combination of these two building blocks is used in a sensitivity-enhanced 2D analog of the 3D TOCSY–TOCSY experiment which provides an efficient tool for resolving severely overlapped signals of oligomers in short experimental time.     

Rotational bands in 181Ta

High-spin states in ¹⁸¹Ta have been studied via the ¹⁷⁶Yb(¹¹B,α2n) reaction at 52 MeV using the PEX array and at 57 MeV using the NORDBALL array, with α-particle detection. The previously known, K^π=(7/2)⁺ ground state band and K^π=(9/2)⁻ band have been extended to spins (29/2)⁺ and (31/2)⁻, respectively. Two new one-quasiparticle bands, the K^π=(5/2)⁺ band built on the known (5/2)⁺ isomer and a K^π=((1/2)⁻) band have been observed. Two other rotational bands with three-quasiparticle structure, K^π=(15/2)⁻ and ((19/2)⁺ with π(7/2)[404]ν²(1/2)[510](9/2)[624] and π(9/2)[514]ν²(1/2)[510](9/2)[624] configurations, respectively, have been newly observed. The half-life of the K^π=((19/2)⁺) bandhead which decays to the head of the (15/2)⁻ band has been measured to be 140(36) ns. However, transitions from the ((19/2)⁺) state to the (15/2)⁻ band have not been observed. Received: 26 August 1998     

Banana-shaped molecules peculiarly oriented in a magnetic field: (2)H NMR spectroscopy and quantum mechanical calculations.

The orientational properties of the banana-shaped liquid crystal 4-chloro-1,3-phenylenebis{4-[4'-(10-undecenyloxy)]benzoyloxy} benzoate (ClPbis11BB) are reported in the nematic phase under the effect of an external magnetic field. A new hypothesis, which states that the central ring of the aromatic core is oriented perpendicularly to the external magnetic field, is proposed. In support of this hypothesis, a series of studies based on (2)H NMR spectroscopy, both in the bulk and in solution, are discussed. (2)H NMR measurements on three selectively deuterium-labelled isotopomers are presented, together with DFT results from B3LYP/cc-pvDz calculations performed on the aromatic core. The rather flat shape of the investigated intramolecular energy surface allows for several different conformations to be populated, the computed magnetic susceptibilities of which are consistent with the proposed hypothesis of peculiar orientation of banana-shaped molecules. Moreover, the orientation of the magnetic susceptibility tensor is shown to be strongly dependent on the internal conformation of the banana-shaped molecules.     

Enthalpimetric and thermometric determination of some nitrogen containing bases and some physiologically active alkaloids

Summary The enthalpimetric determination of a series of bases by using the reaction of the bases and sodium tetraphenylboron is described. The accuracy of the method is analytically acceptable, over the range 3×10^–5 moles to 7.5×10^–4 moles. The upper limit is determined by the bulk of the precipitate.Dosage forms of some physiologically active alkaloids contain more than the upper limit of analyte. Yet, preliminary investigations using silicotungstic acid indicate that this is suitable for thermometric titrations.

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Enthalpimetrische und thermometrische Bestimmung stickstoffhaltiger Basen und physiologisch aktiver Alkaloide

Zusammenfassung Die enthalpimetrische Bestimmung einiger N-haltiger Basen erfolgte aufgrund der Reaktion mit Natriumtetraphenyloborat. Die Genauigkeit ist im Bereich von 3 · 10^–5-7,5 · 10^–4 Mol befriedigend. Eine obere Grenze der Anwendbarkeit ergibt sich aus der Menge des anfallenden Niederschlags. Diese wird bei der Bestimmung von Formulierungen einiger physiologisch aktiver Alkaloide überschritten. Jedoch ist in diesem Fall eine thermometrische Titration mit Hilfe von Silicowolframsäure möglich.

Lecture presented at Euroanalysis I Conference, 28. 8.–1. 9. 1972 in Heidelberg, Germany.     

A rapid enthalpimetric method for the assay of the reducing sugar content of some soft drinks

An enthalpimetric method for the rapid, low cost assay of reducing sugars in soft drinks is reported. The assay involves the determination of the sugars by oxidation with copper(III) ions in an alkaline medium. Separation of the various matrix materials, fruit peel, preservatives, etc. is not required. Amounts of glucose in the range 12.5–50 mg per litre of sample have been determined with an average error of 1.5%. The time of assay is less than 2 minutes. The method is capable of being automated for use with semi-skilled operatives. The proposed method has been compared with the Official Method and the results are equally acceptable. The advantages of the proposed method include speed of assay, the potential for automation and the low cost of individual assays.     

Thermometric titrations at elevated temperatures

The oxidizing power of hexacyanoferrate(III) in alkaline conditions is wellknown. Unfortunately many if its oxidation reactions are too slow at room temperatures for direct titrimetric procedures. A method has been developed for the determination of millimolar amounts of selenium(IV), arsenic(III), antimony(III), chromium(III), and thallium(I) using thermometric titrimetry at approximately 330 K. The reproducibility and accuracy of the method are approximately 1%.     

Simple Analytical Model Predicting Some Features of the Electrolytic Steel-Pickling Process

Electrolytic pickling of steel with neutral solutions, to remove the surface scale, reduces the need for the use of strong acids as needed in conventional pickling. This study is a step towards a more in-depth understanding of the factors affecting the former process. A theoretical model, sufficiently simplified to allow analytical solution, is developed and evaluated to provide a first approximation of the potential and current distributions in the electrolyte and steel band. To gain knowledge and validate the model, a small electrolytic pickling cell is constructed, and experiments, including bubble generation and motion observation, are conducted. The experimental work has shown the remarkable bubble production and adherence to the surfaces, and its effects on reducing pickling efficiency and uniformity. The pickling efficiency is about 30%, confirming other researchers" results. The analytical model shows trends very similar to those observed in the experiments, and provides very valuable guidance. It shows, for example, that the current efficiency decreases as the electrode–band distance increases, and it increases with the band thickness and the band-to-electrolyte conductivity ratio. The energy efficiency decreases by orders of magnitude faster than the current efficiency with all of the above-mentioned parameters, because of the correspondingly strong drop in the band–surface potential. A large amount of current is lost due to interelectrode short circuiting.     

Rapid analysis of dosage forms of some pharmaceuticals by nonaqueous thermometric titrimetry

The use of the technique of solution thermochemistry is proposed for the rapid assay for quality control and quality assurance of dosage amounts of some ethical formulations of some antimalarial drugs. The active ingredients are chloroquine, hydroxychloroquine, dapsone, proguanil hydrochloride, and pyrimethamine.Assay is done without the separation of the excipients and without isolation or derivatisation of the analytes. The titrations are done in glacial acetic acid and utilise the catalysed hydrolysis of acetic anhydride by perchloric acid to indicate the endpoint of the reactions.The time taken for a typical assay, of a typical dosage amount is about 3–5 minutes. The reproducibility is of the order of 1% for the milligramme amounts of analyte present in the dosage amounts of the drugs.

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Zusammenfassung Es wird die Anwendung eines lösungsthermochemischen Verfahrens zu Schnellbestimmungen bei der Qualitätskontrolle und — sicherung von Wirkstoffeinsatzmengen einiger rezeptpflichtiger Präparate von einigen antimalarischen Arzneimitteln empfohlen. Die aktiven Bestandteile sind Chloroquin, Hydroxychloroquin, Dapson, Proguanilhydrochlorid und Pyrimethamin.Die Bestimmungen werden ohne jegliche Abtrennung der Bindestoffe und ohne Isolierung oder Derivatisierung der zu bestimmenden Substanzen durchgeführt. Die Titrierungen werden in Eisessig durchgeführt und bedienen sich der katalytischen Hydrolyse von Essigsäureanhydrid durch Perchlorsäure als Endpunktindikation der Reaktion.Die Dauer für eine typische Probe bei einer typischen Wirkstoffmenge beträgt etwa 3–5 Minuten. Die Reproduzierbarkeit liegt in der Größenordnung von 1% für Milligrammengen der zu analysierenden Stoffe im Arzneimittel.

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We acknowledge the Nigerian Government for the provision of a grant to one of us (S.I.A.). We acknowledge the following for the gifts of samples of the authentic drugs and the tablets assayed in this work: Imperial Chemical Industries plc; May and Baker plc; Winthrop Laboratories plc; Wellcome Foundation (Medical Division).