Unusual Facial Selectivity in the Cycloaddition of Singlet Oxygen to a Simple Cyclic Diene(1)

Syntheses of 5-isopropyl-1,3-cyclohexadiene and syn-5-isopropyl-2,3-dioxabicyclo[2.2.2]octane, by routes that would allow completely diastereoselective introduction of deuterium labels, are described. The reaction of the isopropyl cyclohexadiene with singlet oxygen is shown to give an endoperoxide that is derived by preferential attack on the more sterically hindered face of the diene. A possible mechanistic explanation of this result is that the attack from the less hindered face leads to "ene" reaction rather than endoperoxide formation. However, this mechanism would require that the "ene" reaction and cycloaddition proceed via a common intermediate-presumably a perepoxide.     

New Environmental Applications of Radiation Technology

New environmental applications of radiation technology developed in the laboratory of the author are considered. They include the electron-beam and coagulation purification of molasses slops from a distillery that produces ethanol by fermentation of plant raw materials, the removal of petroleum products (diesel fuel, motor oil, and residual fuel oil) from water by -irradiation, and the electron-beam treatment of multicomponent natural gas mixtures of lower hydrocarbons for the purpose of condensation.     

Synthesis and studies of CuHg(NCX)4 (X = S,Se) and their complexes and application of the softness parameter in the elucidation of their structure

Complexes of CuHg(NCS)₄, CuHg(NCS)₂ (NCSe)₂ and CuHg(NCSe)₄ with tetrahydrofuran, dioxane, pyridine, 2-aminopyridine, nicotinamide, bipyridine and phenanthroline have been prepared and comparative studies made. Bipyridine and phenanthroline form cationic—anionic [CuL₃]²⁺ [Hg(SCN)₄]^2? (L = bipy, phen) complexes with CuHg(NCS)₄ and dinuclear bridged complexes with CuHg(NCSe)₄ and CuHg(NCS)₂ (NCSe)₂. For other ligands the nature of the complexes is binuclear or polynuclear. The comparative stability of the -XCN- bridge (X = S, Se) is CuHg(NCSe)₄ > CuHg(NCS)₂ (NCSe)₂ > CuHg(NCS)₄.     

Zum mechanismus des strahlenchemischen abbaus von polytetrafluorethylen

The present work studies the changes in polymer structure and the mechanism of the decomposition of polytetrafluoroethylene resin (PTFE) exposed to high energy radiation (electron beam). Spectroscopic and kinetic observations are used to interpret the degradation process. For the first time the decomposition of PTFE has been carried out on a preparative scale and new results obtained by analysing the degradation products. The radiation-induced degradation of PTFE is accompanied by thermal degradation under certain irradiation conditions. This is due to an increase in temperature of the polymer caused by retardation of highly accelerated electrons (heat accumulation effect).The kinetics are discussed in terms of the reactions and recombination of radicals produced by high-energy radiation both in the polymer melt and the polymer surface. These are related to the overall rate of decomposition.The primary radicals formed by decomposition of PTFE in an inert atmosphere (N₂, Ar) react to produce perfluorinated alkanes and alkenes. In the presence of reactive gases the decomposition fragments originated will react rapidly; e.g. if oxygen is present in the reactive area the radicals form perflourinated peroxyl and oxyl radicals which finally stabilize themselves by CC-scission to perfluorocarbon acid fluorides and carbonyldifluorides.     

Membrane osmometry of aqueous micellar systems

Summary The number average micellar molecular weights,M _n , were determined with the application of membrane osmometry, for various nonionic and a cationic surfactant, in aqueous solutions. These results show that these micelles are monodisperse, as also reported by other investigators. The dependence ofM _n on temperature was also studied. It was found that both the nonionic and the cationic micelles showed an abrupt change in logM versus temperature plots. In the case of nonionics, the abrupt change was observed at approximately 30 °C lower than the cloud-point.Presented at the 25th Colloid-Meeting in Munich, October 13–15, 1971.     

Chromatographic separation of cannabinoids and their monooxygenated derivatives.

delta1-Tetrahydrocannabinol, delta6-tetrahydrocannabinol, cannabinol, cannabidiol and several of their monooxygenated derivatives have been separated from each other by a combination of liquid, thin-layer and gas chromatography. Retention volumes (on Sephadex LH-20), Rf values and retention times can be recorded, and may provide guidance in the separation and identification of these known cannabinoids.     

Thermodynamic and physical properties of carbon tetrachloride + sulfolane mixtures

The solid + liquid phase diagram, drawn from thermal and dielectric measurements, is presented. It exibits a miscibility gap at 0.08 ≤ χ₂ ≤ 0.58, and two eutectics. The occurrence of a (likely 1:1) intermediate compound, which decomposes on melting into two immiscible liquids, is postulated. Mixed crystals are observed in the sulfolane richer region.Deviations of the liquid mixtures from ideality, positive in the case of viscosity and negative in the case of dielectric constants, are evidenced.     

Mechanism of the radiolytic transformations of cellulose 1. Formation and transformation of radicals

The formation (77K) and transformation (300K) of radicals in celluloses with various degrees of crystallinity under -radiation have been studied by the ESR method. The radical products of the low-temperature -radiolysis of cellulose formed in the polymer chain are macroradicals the unshared electrons of which are localized on C₍₁₎ C₍₄₎, O_(O), and C₍₅₎. With a rise in the temperature to 300K they undergo substantial changes, which shows the dominating role of secondary reactions of macroradicals in the radiation-chemical transformation of cellulose.A. S. Sadykov Institute of Organic Chemistry, Academy of Sciences of the Republic of Uzbekistan, Tashkent, fax (3712) 62 70 71. Translated from Khimiya Prirodnykh Soedinenii, No. 4, pp. 587–595, July–August, 1996. Original article submitted February 26, 1996.     

High-performance liquid chromatography – atmospheric pressure negative chemical ionisation – mass spectrometry of 2,4-dinitrophenyl derivatives of amines

High-performance liquid chromatography (HPLC) coupled to mass spectrometry (MS) is used to detect 2,4-dinitrophenyl (DNP) derivatives of amines by means of negative chemical ionisation at atmospheric pressure. The high sensitivity and good comparability of UV- and MS-detection of DNP-derivatives of amines is shown by several examples. The high selectivity of the derivatisation and the detection method (UV and MS) is used for the analysis of unknown amines in aqueous phases after hydrolytic degradation of polyamide-amine- or polyamine-epoxide-adducts as well as for the characterisation of commercial products.