Synthesis of 1,2-Divinyloxypropenes from Glycerol and Acetylene in the Superbasic System CsF-NaOH-DMSO

Russian Journal of Organic Chemistry -     

Reactivity of Arylhydrazones toward Molecular Oxygen

The kinetics and mechanism of reaction of arylhydrazones with molecular oxygen were studied by gas volumetry. The reaction rate was studied in relation to the structure of arylhydrazone and kind of the solvent. The inhibiting power of the compounds toward initiated oxidation of ethylbenzene was evaluated, and the most effective compounds were found, judging from the ratio of the rate constants of the reactions with molecular oxygen and with peroxy radicals arising in the course of ethylbenzene oxidation.     

New Procedure for Determining the Solubility of Lypophilic Nonionic Surfactants in Water

The procedure that allows to study the kinetics of a dissolution of oleophilic nonionic surfactants in water and to determine the equilibrium values of solubility (S ^eq _w) was proposed, based on the spectrophotometry of extremely dilute, finely dispersed o/w emulsions of these substances prepared by sonication. The equilibrium values of solubility of tetraethoxylated p-nonylphenol (Neonol AF_9-4) and sorbitan monolaurate (Span-20) at 293 K in water are 3.67 × 10^–5 and 1.03 × 10^–5 M, respectively. For the tetraethoxylated p-nonylphenol, the equilibrium value of solubility in water determined by the proposed procedure agrees well with that determined by precision tensiometric measurements.     

Reactions of diterpenoids on solid supports II. Behavior of di- and tricyclic diterpenoids on alumina containing oxidants

The behavior of epimanool (1), epimanool oil, larixol (2), cis-abienol (3) and methyl dehydroabietate (4) on alumina impregnated with oxidants (H₂CrO₄ and KMnO₄) has been studied. This has led to the methyl ketone (5) and norambrenolide (8) - precursors of the perfume substances 14,15,17-trinorlabdane-8,13-dione (6), 8-hydroxy-14,15-bisnorlabd-II-en-13-one (7), and methyl 7-oxodehydroabietate (14). -Levantenolide (11) has been synthesized in one stage from cis-abienol (3)for the first time.Novosibirsk Insitute of Organic Chemistry, Siberian Division of the Russian Academy of Sciences. Translated from Khimiya Prirodnykh Soedinenii, No. 2, pp. 229–234, March-April, 1995. Original article submitted July 25, 1994.     

Classification of heavy-metal fluorides. fluorides with fluorite-like cation arrangement

The main feature of fluorite structure type is four families of crystallographic planes with dense trigon cation nets which are mutually oriented as the faces of a regular octahedron. A complicated cation composition may cause lowering of general symmetry to tetragonal (only one four-fold axis remains in the octahedral complex), rhombohedral (one three-fold axis), orthorhombic, and monoclinic. The geometric parameters of the cation sublattice remain constant. They are close to the parameters of the ideal face-centered cubic cation sublattice of fluorite (the measure of similarity is 1.00–0.81). This is true for all analyzed fluoride structures and some U⁴⁺, Th⁴⁺, Zr, and Ln oxyfluorides. Thus, the concept is confirmed that the crystalline state is determined by systems of parallel planes filled by dense heavy-atom nets. Institute of Inorganic Chemistry, Siberian Branch, Russian Academy of Sciences. Institute of Crystallography, Russian Academy of Sciences. Translated fromZhurnal Struktumoi Khimii, Vol. 35, No. 1, pp. 71–80, January–February, 1994. Translated by T. Yudanova     

Determination of enthalpies of formation of organic free radicals from bond dissociation energies 2. Halosubstituted radicals

The enthalpies of formation (ΔH _f ^o) for 23 halosubstituted radicals were determined from the published data on bond dissociation energies. The ΔH _f ^o values of the corresponding molecules necessary for the calculation of ΔH _f ^o of the radicals were taken from handbooks or calculated by the additive-group method. The conjugation energies of the radicals are calculated, and the effect of substituents at the π-system on these values was shown. Errors of determination of the ΔH _f ^o values of the radicals were estimated. For Part 1, see Ref. 1. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 4, pp. 643–646, April, 1998.     

Kinetics and Mechanism of Monomolecular Heterolysis of Commercial Organohalogen Compounds: XXVIII. Effect of the Nature of the Verdazyl Indicator on Salt Effects in Dehydrobromination of 3-Bromocyclohexene in Nitrobenzene

The salt effect on the rate of dehydrobromination of 3-bromocyclohexene in PhNO2 depends on the nature of the verdazyl indicator. With triphenylverdazyl and its chloro and nitro derivatives in the presence of Et₄NClO₄, a normal salt effect is observed, in the presence of bromides, a superposition of normal and special salt effects, while in the presence of chlorides, a superposition of normal and special negative salt effects. With the dimethoxy verdazyl derivative, a normal salt effect is always observed.     

Simultaneous comparison of δ31P and 1JPN for the assignment of E/Z-stereochemistry of the phosphorus-nitrogen double bond in iminophosphines R-P=N-R′

 The analysis of ³¹P and ¹⁵N NMR data of a series of 40 iminophosphines R-P=N-R′ reveals that the E/Z-stereochemistry of the PN double bond can be predicted on the basis of a simultaneous comparison of the values of δ³¹P and ¹J_PN. Received: 31 May 1996/Revised: 2 July 1996/Accepted: 5 July 1996