Synthesis and Antiviral Properties of Spirocyclic [1,2,3]‐Triazolooxazine Nucleosides

An efficient synthesis of spirocyclic triazolooxazine nucleosides is described. This was achieved by the conversion of β‐D ‐psicofuranose to the corresponding azido‐derivative, followed by alkylation of the primary alcohol with a range of propargyl bromides, obtained by Sonogashira chemistry. The products of these reactions underwent 1,3‐dipolar addition smoothly to generate the protected spirocyclic adducts. These were easily deprotected to give the corresponding ribose nucleosides. The library of compounds obtained was investigated for its antiviral activity using MHV (mouse hepatitis virus) as a model wherein derivative 3 f showed the most promising activity and tolerability.     

Tritium nuclear magnetic resonance spectroscopy—I: Technique,internal referencing and some preliminary results

Routine measurement of triton magnetic resonance spectra is described for the first time, using a micro-bulb sample tube assembly to obviate radiological hazards. Levels of isotope abundance and chemical concentration, the problem of self-radiolysis and the general usefulness of the technique are discussed. Results are given for a selection of compounds including glucose, amino-acids, thymidine and uridine. The self-radiolysis of the last is followed.     

Yttrium complexes incorporating the chelating diamides [ArN(CH2)xNAr]2- (Ar = C6H3-2,6-iPr2, x= 2, 3) and their unusual reaction with phenylsilane

Novel yttrium chelating diamide complexes [(Y[ArN(CH(2))(x)NAr](Z)(THF)(n))(y)] (Z = I, CH(SiMe(3))(2), CH(2)Ph, H, N(SiMe(3))(2), OC(6)H(3)-2,6-(t)Bu(2)-4-Me; x = 2, 3; n = 1 or 2; y = 1 or 2) were made via salt metathesis of the potassium diamides (x = 3 (3), x = 2 (4)) and yttrium triiodide in THF (5,10), followed by salt metathesis with the appropriate potassium salt (6-9, 11-13, 15) and further reaction with molecular hydrogen (14). 6 and 11(Z = CH(SiMe(3))(2), x = 2, 3) underwent unprecedented exchange of yttrium for silicon on reaction with phenylsilane to yield (Si[ArN(CH(2))(x)NAr]PhH) (x = 2 (16), 3) and (Si[CH(SiMe(3))(2)]PhH(2)).     

Tritium nuclear magnetic resonance spectroscopy. 14—analysis of tritiated methyl groups

The complete analysis of the tritium distribution in tritiated methyl groups in labelled compounds is achieved by a direct method for the first time, through ³H NMR spectroscopy aided by resolution enhancement.     

Isomeric forms of tris-Schiff base complexes of iron(II): structure of the complex derived from 2-acetyl pyridine and methylamine

Summary The structure of the tetrahydrate of the nitroprusside salt of the tris-ligand-Fe^II complex of the Schiff base derived from 2-acetyl pyridine and methylamine has been established by x-ray diffraction methods. The cation has themer-configuration in this salt in the solid phase. Kinetic and spectroscopic, particularly¹H n.m.r., results indicate that bothmer-andfac-isomers of this, and of related complexes, have to be considered in solution. Kinetics of base hydrolysis of the title cation, and its solvation, in MeOH-H₂O mixtures are described and compared with those for other low-spin Fe^II-diimine complexes.     

Selective, stability-indicating assay of the major ipecacuanha alkaloids, emetine and cephaeline, in pharmaceutical preparations by high-performance liquid chromatography using spectrofluorimetric detection

A selective high-performance liquid chromatographic procedure has been developed for the determination of the major Ipecacuanha alkaloids, emetine and cephaeline, in a number of linctus and pastille preparations. The reversed-phase chromatographic procedure uses an octadecyl-bonded column with a mobile phase of aqueous methanol containing an ion-pairing reagent. A spectrofluorimetric detector is used for increased sensitivity and selectivity. Sample preparation is simple, involving either straight dilution for linctus formulations or simple dissolutions for pastilles. The procedure has been shown to be stability-indicating. Validation studies, to show that the method is precise, accurate and rectilinear, have been carried out on four linctus formulations and two pastille formulations. The method has been used to determine both emetine and cephaeline at levels as low as 5 micrograms/g in formulations.