Mass-spectrometric study of nitro derivatives of 2(4)-azafluorenes and 2(4)-azafluorenones

The dissociative ionization of 13 nitro derivatives of 2(4)-azafluorenes and 2(4)-azafluorenones was investigated. The introduction of an electron-acceptor nitro group into the molecule markedly reduces the stability of the molecular ions and suppresses the fragmentation pathways that are characteristic for azafluorenes. Nitro-nitrite rearrangement proceeds more readily in nitro-substituted 4-azafluorenes than in nitro-substituted 2-azafluorenes. A characteristic feature of the fragmentation of azafluorenes that do not contain nitro and methyl groups in a vicinal orientation is elimination of a OH particle by the molecular ions. It was established by deuterium labeling that in this case the formation of an [M — OH]⁺ ion is due to the presence of a methylene group attached to the C₉ atom in the molecule.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 7, pp. 941–947, July, 1981.     

Mass-spectrometric study of 4-azaphenanthrene derivatives

The mass spectra of 15 compounds of the 4-azaphenanthrene series and their deutero analogs with bulky R substituents (R=-CCPh, -CH=CHPh, CHBr-CHBrPh,-CH=CHC₆H₄OCH₃-p, -COOH, -COOC₂H₅, and -CONHNH₂) in the ortho position relative to the nitrogen atom were studied. An intense [M-H]⁺ ion peak, the appearance of which is evidently due to a process involving cyclization of the carbon atom of the side chain with the nitrogen atom, is formed in the fragmentation of the styryl derivatives. The fragmentation of the compounds with a methyl group in the ortho position relative to the styryl grouping is accompanied by the formation of an intense [M-Ph]⁺ ion peak. An ortho effect of the carboxyl and carbethoxy groups adjacent to the methyl substituent is observed in the mass spectra of the investigated compounds. The data obtained make it possible to establish the structures of bulky substituents in the ortho position relative to the ring nitrogen atom and the position of the methyl group in the pyridine ring of monomethylated azaphenahthrenes.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 5, pp. 659–665, May, 1979.     

Mass-spectrometric study of methyl-substituted azomethines of the 4-azafluorene series

The M⁺ and [M-H]⁺ ion peaks are the peaks of maximum intensity in the mass spectra of Schiff bases belonging to the 4-aza-9-fluorenylidenearylamine series. The dependence of the relative intensity of the [M-H]⁺ fragment on the structures of the I–XI molecules provides evidence for the possibility of the occurrence of rearrangement processes involving the formation of this ion. The formation of [M-CH₃]⁺, [M-HCN]⁺, [M-Ar]⁺, and [M-CNAr]⁺ ions is also characteristic for the fragmentation of the investigated compounds. It was found that, in contrast to other types of Schiff bases, the ejection of an HCN molecule during the mass-spectrometric fragmentation of the investigated compounds occurs without participation of the nitrogen atom of the azomethine group. The elimination of a CNAr particle by the molecular ions is a distinctive feature of the investigated series of Schiff bases.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 3, pp. 397–402, March, 1979.     

Comonotone approximation of periodic functions

Suppose that a continuous 2π-periodic function f on the real axis ? changes its monotonicity at different ordered fixed points y _i ∈ [? π, π), i = 1, …, 2s, s ∈ ?. In other words, there is a set Y:= {y _i } _i∈? of points y _i = y _i+2s + 2π on ? such that, on [y _i , y _i?1], f is nondecreasing if i is odd and nonincreasing if i is even. For each n ≥ N(Y), we construct a trigonometric polynomial P _n of order ≤ n changing its monotonicity at the same points y _i ∈ Y as f and such that $$ \left\| {f - P_n } \right\| \leqslant c\left( s \right)\omega _2 \left( {f,\frac{\pi } {n}} \right), $$ where N(Y) is a constant depending only on Y, c(s) is a constant depending only on s, ω ₂(f, ·) is the modulus of continuity of second order of the function f, and ∥ · ∥ is the max-norm.     

Sorption of bismuth(iii) and its chloride complexes with 2-aminopyrimidine cation on hydroxyapatite of various textures

Russian Chemical Bulletin - Specific features of the interaction between bismuth(iii) and hydroxyapatite (HAP) of various morphologies during its sorption and co-crystallization binding were...     

Parametric excitation of magnetoelastic vibrations in hematite single crystals in weak magnetic fields

This paper reports on the results of investigations into the magnetoelastic vibrations excited by radio pulses in thin single-crystal hematite plates according to the scheme of parallel parametric pumping. It is demonstrated that this technique can be used to examine the multimode spectrum of natural vibrations of crystals in weak external magnetic fields H₀ < 200 Oe and to measure some acoustical quantities in this range. By using the parametric amplification of sound, it is established that an increase in the magnetic field is accompanied by the appearance of weakly damped low-intensity modes in the spectrum of natural vibrations.     

X-ray diffraction studies of 6-methyl-5-acetyl-4-α-furyl-2-keto-1,2,3,6-tetrahydropyrimidine and 6-methyl-5-acetyl-4-γ-bromophenyl-2-thio-1,2,3,6-tetrahydropyrimidine

6-Methyl-5-acetyl-4-α-furyl-2-keto-1,2,3,6-tetrahydropyrimidine (I) and 6-methyl-5-acetyl-4-γ-bromophenyl-2-thio-1,2,3,6-tetrahydropyrimidine (II) are prepared by the modified Biginelli reaction, and their crystal and molecular structures are studied. It is shown that, in crystals I and II, the pyrimidine ring has an amide tautomeric form and adopts a sofa conformation. The IR absorption spectra are analyzed, and the stability of the tautomers of the pyrimidine fragments is evaluated using quantum-chemical calculations.     

Comonotone Jackson's Inequality

Let 2s points y_i=−πy_2s<…<y₁<π be given. Using these points, we define the points y_i for all integer indices i by the equality y_i=y_i+2s+2π. We shall write fΔ⁽¹⁾(Y) if f is a 2π-periodic continuous function and f does not decrease on [y_i, y_i−1], if i is odd; and f does not increase on [y_i, y_i−1], if i is even. In this article the following Theorem 1—the comonotone analogue of Jackson's inequality—is proved. 1. If fΔ⁽¹⁾(Y), then for each nonnegative integer n there is a trigonometric polynomial τ_n(x) of order n such that τ_nΔ⁽¹⁾(Y), and |f(x)−π_n(x)|c(s) ω(f; 1/(n+1)), x , where ω(f; t) is the modulus of continuity of f, c(s)=const. Depending only on s.     

Nuclear Magnetic Resonance Spectra of Polyhydroxylated Fullerene C60(OH)n

Polyhydroxylated fullerene C₆₀(OH)_n (with an estimated number of hydroxyl groups n = 38–44) synthesized from pure fullerene by mixing a benzene solution of C₆₀ with a NaOH aqueous solution in the presence of a catalyst was studied with ¹H and ¹³C solid-state nuclear magnetic resonance. Possible features of the structure of a molecule shell were revealed from ¹H NMR data. The ¹³C spectrum showed a peak splitting with an increase in temperature, which is probably due to fullerenol isomers.