Nitroxydes—LXXVI: Couplages a longue distance dans les nitroxydes azatricycliques. etude par rpe et rmn. conformation du groupement nitroxyde

Complete determination of all proton hyperfine splitting constants in magnitude and sign, and their specific assignment in two stable rigid nitroxides are presented. Long range γ-splitting has been calculated by an MO method (INDO approximation) and by a modification of a valence bond calculation. The results are consistent with a non-planar and rapidly inverting NO group.     

Fluoroaliphatic esters of fluorosulfonic acid. 4. Reactions of α-fluorosulfatoperfluoro ketones with nucleophilic reagents

-Fluorosulfatoperfluoroethyl isopropyl ketone I and fluorosulfatopentafluoroacetone II react with alkali metal chlorides and bromides to form the corresponding -haloperfluoro ketones as a result of direct nucleophilic substitution.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 9, pp. 2066–2069, September, 1990.     

Magnetic resonance studies of the deuteration effect on intersystem crossing in the anthracene molecule

The intersystem crossing decay constants from the ³B_2u state into the ground state of anthracene-d₁₀ in a phenazine crystal have been determined by magnetic resonance techniques at 1.5°K both at high magnetic field and, by a parameterization procedure, at zero magnetic field. A comparison of the anthracene-d₁₀ zero-field results with those for anthracene-h₁₀ show the effects of deuterium substitution to be largest for the in-plane spin levels of the anthracene triplet state.     

Discussion on the method for the measurement of the flexural modulus of coupled materials and reasons of the shifts of theQ −1 maxima caused by coupling

Summary When measuringQ ^–1 and the flexural resonance frequency of bars clamped at one end, constituted by a viscoelastic polymeric material glued to a rigid support of modulusE ₁, it is possible to calculate the componentsE ₂ andE ₂ of the complex elastic modulus of the polymeric material examined. In this work the minimum (critical) value of the ratioa=E ₂ /E ₁=a _c and the values of the ratioQ ₂ ^–1/Q ^–1=F ₁ are evaluated beyond which no exact calculation ofE ₂ and ofQ ₂ ^–1 is possible.Within the confidence limits of the linear viscoelasticity theory, these values depend on the accuracy of measurement of both frequency and resonance curve, as well as on the instrument employed, on the operating temperature and on the ratio between the thicknesses of the two coupled materials.In order to keep outside the critical conditions, the most convenient method involves the use of measurements of coupled test-pieces having different ratiosz between their thicknesses and of supports having different modulusE ₁, depending on the field of temperature of the analysis ofE ₂ and tg ₂ concerning and E.P.R. elastomer and a vulcanized cis-1,4 polyisoprene in very wide ranges of temperature comprising the glass transition. Moreover, it is demonstrated by analysis the shift on the temperature axis of the tg maximum of the composite test-piece with respect to the position of the tg maximum of the polymeric material alone.With 11 figures and 1 table     

Reaction of 2-methylene-3-oxoquinuclidine with nucleophilic reagents

The salts and quaternary derivatives of 2-methylene-3-hydroxyquinuclidine readily add nucleophilic reagents because of the high polarity and polarizability of the carbon-carbon double bond, which are due to the overall electron-acceptor effect of the positively charged nitrogen atom and the carbonyl group. The double bond is substantially deactivated in the base, and the addition of nucleophilic reagents is hindered.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 10, pp. 1370–1376, October, 1977.