Identification of radicals spin-trapped in autoxidized linoleic acids: A high performance liquid chromatography and electron spin resonance study

Radicals generated in linoleic acid and deuterated linoleic acid have been trapped by the spin trap 2-methyl-2-nitroso-propane (MNP) and identified by electron spin resonance (ESR) and ENDOR spectroscopy. The formation of two distinct secondary alkyl radical adducts (one conjugated, the other non-conjugated, as shown by their UV absorption spectra) was demonstrated by 11, 11-dideuterio-9-cis-12-cis-linoleic acid using HPLC and ESR spectroscopy.     

Ferrimetric determination of uranium using rhodamine 6G as fluorescent indicator

Experimental conditions have been developed for the titration of uranium^IV with iron^III alum solution, using Rhodamine 6G as a fluorescent indicator. The titration is best carried out at 98–100° in a 2–3N hydrochloric acid medium, under filtered ultraviolet light, using 2.0 ml of 0.05% Rhodamine 6G solution for 30 ml of the titration mixture. A slight excess of iron^III solution quenches the greenish-yellow fluorescence of the dye through inner filter action. With the titration assembly described here, it is possible to determine uranium^IV with an accuracy of about 0.4%. This method appears to be more convenient than the potentiometric titration or the method employing potassium thiocyanate as internal indicator.

Evidence is also presented to show that the reaction between uranium^IV and iron^III is slow at room temperature.     

Spectrophotometric methods for the determination of tamoxifen citrate

Three simple and sensitive spectrophotometric methods for the determination of tamoxifen citrate have been developed. They are based on the formation of an ion-association complex between the drug and a dye, Erioglaucine A, which is extractable into chloroform and has an absorption maximum at 625 nm (method A), oxidation with excess potassium permanganate and the determination of unconsumed permanganate using Fast Green FCF (method B), or by the formation of a coloured cobalt thiocyante coordination complex which is extracted into benzene and measured at 635 nm (method C). Beer's law limits for methods A, B, and C are 0.5-3.0 mug ml(-1), 1.0-6.0 mug ml(-1) and 100-500 mug ml(-1), respectively. No interference was observed from tableting additives and the applicability of the methods was examined by analysing tablets containing tamoxifen. The quantities determined were 99.0-100.03% of the exptected values.     

The isolation and structure of 6″-bromo-isoarboreol - the first bromine containing lignan

A new lignan from $\text{Gmelina arborea}$ is shown to be 1, 2a-dihydroxy-2e-piperonyl-6e-(6″-bromopiperonyl)-3, 7-dioxabicyclo-[3,3,0]-octane, the first example of a bromine containing lignan.     

RED EDGE EXCITATION EFFECT IN INTACT EYE LENS

Shift in the wavelength of emission upon shift in the excitation wavelength towards the red edge of the absorption band is termed Red Edge Excitation Shift (REES). This effect is observed only in situation where the fluorophore mobility with respect to the surrounding matrix is considerably reduced. We have observed such red edge excitation effect in the intact eye lens. The REES observed for a normal lens is different from that seen in a photodamaged lens and hence appears to be a potential tool to monitor the changes in the state of the lens. Photodamage experiments with tryptophan in polyethylene glycol (PEG) and intact eye lens indicate that the red edge photon can also cause photodamage.     

Semi-synthesis of paclitaxel from naturally occurring glycosidic precursors

Paclitaxel, an antitumor drug effective on ovarian and breast carcinomas, is currently being produced both by direct isolation from the bark of Taxus brevifolia and by semi-synthesis from a natural precursor, 10-deacetyl baccatin III. Although other potential precursors such as 10-deacetyl paclitaxel-7-xyloside were known since 1984, their conversion to paclitaxel could not be achieved because of the lack of suitable methodology for hydrolyzing the xylose residue, compatible with the stability of the compound. A method is described here using periodate, followed by phenylhydrazine, to effect deglycosidation of 10-deacetyl paclitaxel-7-xyloside to form 10-deacetyl paclitaxel. In addition, by including an intermediate acetylation step before the reaction with phenylhydrazine, “direct” conversion of this xyloside to paclitaxel itself, is described. Because 10-deacetyl paclitaxel-7-xyloside occurs at >0.1% in the bark of Taxus brevifolia, its successful hydrolytic conversion to paclitaxel represents an extremely important reaction for the enhanced availability of this drug.     

Mild oxidation of alcohols with o-iodoxybenzoic acid (IBX) in water/acetone mixture in the presence of beta-cyclodextrin

A mild and efficient oxidation of alcohols with o-iodoxybenzoic acid (IBX) catalyzed by beta-cyclodextrin in a water/acetone mixture (86:14) has been developed. A series of alcohols were oxidized at room temperature in excellent yields.     

Selective imidoylnitrenes

Two new imidoylnitrenes and alkoxycarbonylnitrene form a sequence of reactivities : Only ROCON attacks CH bonds, it and ROC(NCN)N convert benzene to azepines. Benzene is not attacked by ROC(NSO₂CH₃)N, but all three nitrenes react with olefins, alcohols, etc.     

Some studies on thallium oxalates. VI

The effect of the thallium(I) concentration on the potentiometric titration of thallium(III) with oxalic acid in 0.1M HNO₃ or 0.05M H₂SO₄ is studied, and conditions are established for the preparation of the thallium(I) bis-oxalato diaquo thallate(III) complex. Chemical analysis of the salt corresponds to the formula T1^I(T1^III(C₂O₄)₂) · 5 H₂O. Thermal decomposition studies on the complex using TG, DTG and DTA techniques indicate the formation of thallium(I) oxalate (stable from 130° to 320°) as the intermediate, the final product being a mixture of thallium(I) oxide and thallium(III) oxide (stable from 520° to 600°). Infrared absorption spectra, X-ray diffraction patterns and microscopic observations are used to characterise the complex and the intermediate.     

Sc(OTf)3-catalyzed alkylation of indoles with propargyl alcohols: an expeditious synthesis of 3-substituted indoles

Indoles undergo smooth alkylation with propargylic alcohols in the presence of 10 mol % of scandium triflate under mild conditions to produce 3-propargylated indoles in excellent yields with high selectivity.