Synthesis and properties of pyrimidinylalkylsulfonamides 4. Reaction of the Na salt of p-toluenesulfonamide with mono-N-(ω-haloalkyl)uracils

Conclusions The direction of reaction and the composition and yields of products obtained by reaction of the Na salt of p-toluenesulfonamide with N-(-bromoalkyl)uracils depend primarily on the length of the alkyl chain in the latter: When the Na salt of p-toluenesulfonamide reacts with N-(-bromopropyl)-6-methyluracil, the latter undergoes intramolecular cyclization, whereas the Na salt of p-toluenesulfonamide undergoes intermolecular alkylation at the sulfonamide group on reaction with N-(-bromopentyl)-6-methyluracil. In analogous reactions, N-(-bromobutyl)uracils undergo both intramolecular cyclization, followed by opening of the oxazepine ring by nucleophilic reagents, and intermolecular alkylation.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 9, pp. 2079–2084, September, 1978.     

Synthesis of ω-haloalkanoic acids by the catalytic decomposition of cycloalkane hydroperoxides by copper ions

Conclusions The action of catalytic amounts of copper ions in the presence of MX salts (M=K and Na, X=Cl, Br, I, SCN) leads to the decomposition of the hydroperoxides of C₅-C₇ cycloalkanones with the formation of -chloro-,-bromo-, -iodo-, and -thiocyanoalkanoic acids.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 11, pp. 2628–2630, November, 1984.     

Thermodynamic studies of clathrate hydrates

Thermodynamic studies of clathrate hydrates, mainly of structures I and II, are considered in this review which is based on 147 references. There are two main subjects. The first is the host lattice energy and the guest-host interaction energy, both of these quantities being related to the enthalpy of dissociation and composition of the hydrates. The second subject concerns orientational ordering phenomena occurring in both host and guest, as reflected in the low temperature heat capacity. The classical theoretical treatment of clathrate formation has been reconsidered on the basis of recent experimental results. Particular emphasis has been given to orientational ordering since this topic is undoubtedly central to clarifying the nature of clathrate hydrates.Ausgehend von 147 Literaturangaben wurden in diesem Review thermodynamische Untersuchungen von Klathrathydraten hauptsächlich der Struktur I und II betrachtet. Es gibt zwei Hauptaugenmerke. Als erstes die Wirtsgitterenergie und die Gast-Wirt-Wechselwirkungsenergie, beide bezogen auf die Dissoziationsenthalpie und die Bildungsenthalpie der Hydrate. Das zweite Hauptaugenmerk betrifft Orientierungs-Konditionierungserscheinungen sowohl in Wirt als auch Gast, wie in den Wärmekapazitäten bei niedrigen Temperaturen widergespiegelt wird. Auf der Basis jüngster experimenteller Ergebnisse wurde die klassische theoretische Betrachtung über die Bildung von Klathraten überprüft. Der Orientierung-Konditionierung wurde besonderer Nachdruck verliehen, da dies zweifellos eine entscheidende Rolle bei der Klärung der Natur der Klathrathydrate spielt. 147 I II. . «» « — », . «» « », . . , .

---

Contribution No. 155 from the Chemical Thermodynamics Laboratory.     

Diffusion Sensor of Mechanical Signals: Frequency Response at High Frequencies

The frequency response of a diffusion transducer with gauze electrodes, studied theoretically at high frequencies, is proportional to ^-3/2 starting with = D/R ² at < /R ² and to ^-1 at > /R ². Here, = 2f, f is the signal frequency, the electrolyte viscosity, D a diffusion coefficient, and R the radius of the gauze filaments. The calculation is compared with experiment.     

ω,ω′-imino dicarboxylic acids and some of their derivatives

Summary Starting from the corresponding-chloro carboxylic acids we prepared, -imino dicarboxylic acids and their N- and O- derivatives; the products had the following structures:     

Synthesis of modified amino acids containing nucleic acid purine bases

The reaction of hydrazides of adenylyl- or hypoxanthinyl-9-alkylcarboxylic acids with sodium nitrite in acid media gives reactive azides of purinyl-9-alkylcarboxylic acids which condense with ()-aminocarboxylic and ,-diaminocarboxylic acids to give N(N)-(adenylyl-9-alkanoyl) aminocarboxylic, N-(adenylyl-9-)- and N-(hypoxanthinyl-9-alkanoyl)-,-diaminocarboxylic acids. The deamination of N-(adenyl-yl-9-alkanoyl)aminocarboxylic acids gives N-(hypoxanthinyl-9-alkanoyl)aminocarboxylic acids.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 1, pp. 126–130, January, 1985.     

Simple Estimations of Dynamic Polarizabilities and Dispersion Coefficients Using the Spectral Moment Method

A modification of the spectral moment technique is suggested to calculate the frequency-dependent polarizabilities (i ) and ( ) and the corresponding dispersion constants. Unlike the previous schemes, this method uses the spectral moments S _q with positive values of q. Both variational and nonvariational methods are tested. An effective nonvariational procedure is worked out which isolates a regular (odd) component from the Brown–Rebane functional for (i ). Fast convergence to exact values is achieved by using a suitable renormalization of the electron transition pseudospectrum. The method is illustrated by the semiempirical and ab initio calculations of molecular systems of various classes.     

TPD of ammonia from H-ZSM-5 zeolites deactivated during coupled methanol hydrocarbon cracking (CMHC)

The deactivation of H-ZSM-5 zeolite samples during coupled methanol/hydrocarbon cracking (CMHC) with n-butane as feed has been investigated in two different reaction modes (with intermediate regeneration and without regeneration). TPDA was used to characterize strong Brönsted acidity of fresh, regenerated and steamed H-ZSM-5 zeolite. The prevention of dealumination by blocking the acid centers with carbonaceous products could be proved, but the conversion rate of n-butane and the olefin selectivity declined drastically with increasing coking rate. H-ZSM-5 - / - - ( -). , - H-ZSM-5. - , , - - .     

Reaction of the sodium salts of several hydroxypyrimidines withα,ω-dihaloalkanes

Conclusions A simple one-step method for the synthesis of 1,3-bis(-haloalkyl)uracils by reacting the Na salts of uracil and its derivatives with ,-dihaloalkanes has been developed.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 4, pp. 880–884, April, 1977.     

On the synthesis of ω-appended hypericin derivatives

Summary A method for the preparation ofbis--appended hypericin derivatives bearingn-octyl,n-hexadecyl, and 2-(2-(2-hydroxyethoxy)-ethoxy)-ethoxymethyl substituents was developed. The key step — the synthesis of appropriately -substituted emodin derivatives — was achieved by solvolyzing 3-bromomethyl-1,6,8-triacetyloxy-anthracene-9,10-dione (-bromo triacetylemodin) in an appropriate alcohol in the presence of silver perchlorate. The correspondingbis--substituted hypericins were then prepared conventionally by dimerizing the -substituted emodin anthrones. The latter were prepared by reduction of the -appended emodins.

---

Zur Synthese von -substituierten Hypericinderivaten

Zusammenfassung Eine Methode zur Darstellung vonbis--substituierten Hypericinderivaten wurde entwickelt. Der Schlüsselschritt — die Synthese der entsprechenden Emodinderivate — wurde durch die Solvolyse von 3-Bromomethyl-1,6,8-triacetyloxyanthracen-9,10-dion (-Bromtriacetylemodin) im entsprechenden Alkohol in Gegenwart von Silberperchlorat ermöglicht. Die entsprechendenbis--substituierten Hypericinderivate wurden auf konventionelle Weise durch Dimerisierung der -substituierten Emodinanthrone dargestellt. Letztere erhielt man durch Reduktion der -substituierten Emodine.

     

Reaction of the sodium salts of some hydroxypyrimidines with α,ω-dihaloalkanes Communication 4. Synthesis of N-(ω-haloalkyl)uracils

Conclusions A method has been developed for the preparation of 1,3-bis(-haloalkyl)uracils with methylene chains of different lengths in the -haloalkyl radicals in the N¹ and N³ positions of the pyrimidine ring.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 5, pp. 1173–1177, May, 1986.     

Third-Order Nonlinear Optical Response of a New PVA Composite with PbS Nanocrystals

High third-order nonlinear optical susceptibility (⁽³⁾(;, –,)=3.4·10 ^–16 m²/V²) in the visible spectral range may be achieved in PVA composites with narrow-gap PbS semiconductor nanocrystals with a large exciton diameter.