Reaction of chloromethyliso(thio)cyanato(thio)phosphonates(-phosphinates) with phenol,ethanol, and thiols

(Chloromethyl)isocyanatophosphonates(-phosphinates) take up phenol to form carbamates whose -cleavage gives rise to phenyl (chloromethyl)phosphonates(-phosphinates). (Chloromethyl)(thio)phosphinic-(phosphonic) isothiocyanates react with phenol at 20°C in the absence of catalyst to afford phenyl phosphinates(-phosphonates). (Alkylsulfanyl)carbamates formed by addition of thiols to (chloromethyl)iso(thio)cyanastophosphonates(-phosphinates) under the action of an equimolar amount of triethylamine undergo cyclization into 1,3,4-oxaza(thiaza)phospholines.Translated from Zhurnal Obshchei Khimii, Vol. 74, No. 9, 2004, pp. 1441–1446.Original Russian Text Copyright © 2004 by Khailova, Bagautdinova, Shaimardanova, Krepysheva, M. Pudovik, Chmutova, Azancheev, Musin, A. Pudovik.This revised version was published online in April 2005 with a corrected cover date.     

Preparation of micron-size monodisperse polymer microspheres having cationic groups

Micron-size monodisperse crosslinked polymer microspheres having chloromethyl groups were prepared by seeded copolymerization of styrene, divinylbenzene, and chloromethylstyrene in the presence of 2.1- monodisperse polystyrene seed particles produced by dispersion polymerization. The modification reaction of chloromethyl groups on the surfaces with polyamines such as triethylenetetramine and ethylenediamine was carried out. From the measurements of potential and the amount of chloride ion released, the introduction of a large number of cationic groups at the surfaces was confirmed.Part CXXXI of the series Studies on suspension and Emulsion.     

Studies in the field of 2, 1, 3-Thiadiazole and 2,1, 3-Selenadiazole

Benzo-2, 1, 3-thiadiazole (I) undergoes chloromethylation with dichlorodimethyl ether in the presence of anhydrous aluminum chloride with the predominant formation of 4, 7-di(chloromethyl)benzo-2, 1, 3-thiadiazole (II). Bases and pseudobases (paraformaldehyde, hexamethylenetetramine, dimethylformamide) exert an inhibiting influence on this reaction. In the presence of these substances, a mixture of compound II and 4-(chloromethyl)benzo-2, 1, 3-thiadiazole (III) is formed, or else no reaction takes place. The structures of compounds II and III has been shown by their reductive decomposition to o-diamines described in the literature. The high reactivity of the chlorine in the chloromethyl group has enabled various new derivatives of benzo-2, 1, 3-thiadiazole to be obtained by its replacement with hydroxy, thiocyanato, di(-hydroxyethyl)amino, di(-chloroethyl)amino, formyl, and carboxy groups.For communication XLVIII, see [11].     

Controlled tosylation of 1,4:3,6-dianhydro-D-mannitol and -D-sorbitol

Controlled tosylation of 1,4:3,6-dianhydro-D-mannitol and -D-sobitol is studied. The nature of amines that act both as reaction activators and hydrogen chloride acceptors exerts a considerable effect on the ratio and structure of the resulting products.Translated from Zhurnal Obshchei Khimii, Vol. 74, No. 10, 2004, pp. 1739–1742.Original Russian Text Copyright © 2004 by Kurochkina, Bratash, Soboleva, Vasyanina, Grachev, Nifantev.This revised version was published online in April 2005 with a corrected cover date.     

Influence of plasma-electrolytic treatment of titanium on the composition and properties of ruthenium-titanium oxide anodes

Data on elemental and phase composition, morphology, and electrocatalytic behavior in dilute chloride solutions of ruthenium-titanium oxide anodes subjected to preliminary plasma-electrolytic treatment are presented.Translated from Zhurnal Prikladnoi Khimii, Vol. 77, No. 12, 2004, pp. 1968–1973.Original Russian Text Copyright © 2004 by Vasileva, Rudnev, Tyrina, Kondrikov, Kuryavyi, Shchitovskaya.     

Synthesis of bis(chloromethyl) derivatives of diphenyl sulfide,thianthrene, and dibenzothiophene

Conclusions The chloromethylation of diphenyl sulfide, thianthrene, and dibenzothiophene, respectively, gave 4,4-bis(chloromethyl)diphenyl sulfide, 2,6-bis(chloromethyl)thianthrene, and 2,7-bis(chloromethyl)dibenzothiophene.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 12, pp. 2799–2801, December, 1976.     

The standard transported entropy of chloride ion in H2O and D2O

Transported entropies of the chloride ion, , in H₂O and in D₂O at 25°C and at concentrations ranging from 0.001 to 0.04m have been determined from the measurements of the steady-state (final) thermoelectric powers of the silver-silver chloride thermocell. Experimental data was extrapolated to infinite dilution to obtain the standard transported entropy . The concentration dependence of is examined and the solvent-isotope effect on the transported entropy is investigated. Thermodynamic data on the entropy of transfer of chloride ion from H₂O to D₂O is used to estimate the difference of the standard ionic entropy of transport in H₂O and D₂O for chloride ion.     

Elemental sulfur as a stabilizing agent for vinyl chloride polymers

The possibility of stabilization of some vinyl chloride polymers with elemental sulfur in their thermal and thermal oxidative degradation was studied.Translated from Zhurnal Prikladnoi Khimii, Vol. 77, No. 11, 2004, pp. 1877–1879.Original Russian Text Copyright © 2004 by Kolesov, R. M. Akhmetkhanov, Nagumanova, Kabalnova, R. R. Akhmetkhanov, Zaikov.     

Calorimetric study of polyvinyl alcohols used as emulsifiers in suspension polymerization of vinyl chloride

The heat effects of dissolution of two pairs of polyvinyl alcohols used as emulsifiers in suspension polymerization of vinyl chloride and the optical transmission of their stirred aqueous solutions as a function of time were determined.Translated from Zhurnal Prikladnoi Khimii, Vol. 77, No. 11, 2004, pp. 1917–1919.Original Russian Text Copyright © 2004 by Kiryanov, Semchikov, Kronman, Ganyukhina, Leshina, Orekhov.     

New transformations of the reaction product of 4-(dichloromethylene)-2-phenyl-1,3-oxazol-5(4<Emphasis Type="Italic">H</Emphasis>)-one with triphenylphosphine

Consecutive treatment of the available 4-(dichloromethylene)-4-phenyl-1,3-oxazol-5(4H)-one with triphenylphosphine, water, and triethylamine gives a stabilized ylide Ph₃P=CHCONHCOPh. Its structure was proved by X-ray diffraction. The ylide reacts with hydrogen chloride and phosphorus pentachloride to give a many-center phosphonium reagent with a 1,3-dichloro-2-aza-1,3-diene group, which enters cyclocondensations with hydrazine hydrate, phenylhydrazine, and benzamidine. These reactions allowed synthesis of phosphonium salts of the general formula Ph₃ CH₂HtAn^– derived from 1,2,4-triazole or 1,3,5-triazine. The structure of the cyclization products was established by spectral methods, as well as by alkaline dephosphorylation.Translated from Zhurnal Obshchei Khimii, Vol. 74, No. 9, 2004, pp. 1434–1440.Original Russian Text Copyright © 2004 by Brovarets, Golovenko, Sviripa, Zyuz, Chernega, Drach.This revised version was published online in April 2005 with a corrected cover date.     

Reaction of carbon tetrachloride with hydrogen peroxide

Reaction of carbon tetrachloride with aqueous hydrogen peroxide in the presence of anhydrous iron(III) chloride was studied. Optimal conditions for the preparation of phosgene were found on the basis of analysis of the kinetic data and mechanism of the process. The reaction rate and yield (the latter reaching 95% in the stationary mode) are determined mainly by the amount of the heterogeneous catalyst. According to the experimental data, the reaction follows a radical mechanism.Translated from Zhurnal Organicheskoi Khimii, Vol. 40, No. 10, 2004, pp. 1455–1458.Original Russian Text Copyright © 2004 by Tatarova, Trofimova, Gorban, Khaliullin.     

Steric structure of aryl chloromethyl ethers based on electrooptical data

Conclusions p-Substituted phenyl chloromethyl ethers have a conformation with a gauche orientation of the C-Cl and C-O bonds; the aromatic ring is removed from the COC plane by 40°.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 12, pp. 2720–2724, December, 1985.     

Synthesis and NMR spectroscopy of N,N-dialkyl-N' -(dimethyl-chlorosilylmethyl) ureas with an intramolecular Si←O bond

The reaction of N,N-dialkyl-N' -trimethylsilylureas with dimethyl (chloromethyl)-chlorosilane gave N,N-dialkyl-N'-(dimethylchlorosilylmethyl)ureas with an intramolecular SiO bond. Relatively stable N,N-dialkyl-N' -[dimethyl (chloromethyl) silyl]ureas are intermediates. The structures of the compounds obtained were demonstrated by NMR spectroscopy.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 12, pp. 2841–2843, December, 1989.     

Single‐electron‐transfer/degenerative‐chain‐transfer mediated living radical polymerization of vinyl chloride catalyzed by thiourea dioxide/octyl viologen in water/tetrahydrofuran at 25 °C

The single‐electron‐transfer/degenerative‐chain‐transfer mediated living radical polymerization (SET–DTLRP) of vinyl chloride (VC) in H₂O/tetrahydrofuran at 25 °C catalyzed by thiourea dioxide [(NH₂)₂C?SO₂] is reported. This polymerization occurs only in the presence of a basic sodium bicarbonate (NaHCO₃) buffer and the electron‐transfer cocatalyst octyl viologen. The resulting poly(vinyl chloride) (PVC) has a number‐average molecular weight of 1500–7000 and a weight‐average molecular weight/number‐average molecular weight ratio of 1.5. This PVC does not contain detectable amounts of structural defects and has both active chloroiodomethyl and inactive chloromethyl chain ends. Because of possible side reactions caused by the primary sulfoxylate anion (SO), the catalytic activity of (NH₂)₂C?SO₂ in the SET–DTLRP of VC is lower than that of the single‐electron‐transfer agent sodium dithionite. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 43: 287–295, 2005     

A facile synthesis of 5(6)‐(chloromethyl)benzimidazoles: Replacement of a sulfonic acid functionality by chlorine

Valuable new synthetic intermediates, 5(6)‐(chloromethyl)benzimidazoles, were prepared by the facile elimination of sulfur dioxide under the influence of thionyl chloride from benzimidazole‐5(6)‐methane‐sulfonic acids easily obtained from (3,4‐diaminophenyl)methanesulfonic acid with formic‐, or trifluoroacetic acid. Both reaction steps involved only acidic conditions, thus the synthesis of polysubstituted 5(6)‐(chloromethyl)benzimidazoles incorporating base‐sensitive substituents became possible.     

<Emphasis Type="Italic">N</Emphasis>-arylsulfanyl-<Emphasis Type="Italic">N</Emphasis>-arylsulfonyl(acyl)-<Emphasis Type="Italic">N</Emphasis>′-phenylthiourea sodium salts

Reactions of N-arylsulfonyl(acyl)arenesulfenamide sodium salts with phenyl isothiocyanate afforded N-arylsulfanyl-N-arylsulfonyl(acyl)-N-phenylthioura sodium salts which were found to increase thermal stability of finely dispersed poly(vinyl chloride).Translated from Zhurnal Organicheskoi Khimii, Vol. 40, No. 10, 2004, pp. 1532–1535.Original Russian Text Copyright © 2004 by Koval, Oleinik.     

N,N′-Diacylated imidazolidines and hexahydropyrimidines

A method for the preparation ofN-monoacyl imidazolidines and hexahydropyrimidines (as hydrochlorides) by interaction of monoacylated derivatives of ethylenediamine and trimethylenediamine with chloromethyl methyl ether was developed. Also a method for the preparation ofN,N-diacylimidazolidines and hexahydropyrimidines either by acylation of their monoacyl derivatives or by reaction of the correspondingN,N-diacyl alkylenediamine derivatives with dimethoxymethane, diacetoxymethane, 1,3,5-trioxane or chloromethyl methyl ether was designed.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 8, pp. 1452–1456, August, 1994.     

Cluster structure of epoxy-phenolic polymer prepared by curing a mixture of epoxy-4,4′-isopropylidenediphenyl and phenol-formaldehyde oligomers

The kinetics of viscosity variation and the concentration and kinetic modes of precondensation of a mixture of epoxy-4,4-isopropylidenediphenyl and phenol-formaldehyde oligomers in Cellosolve solutions in the presence of phosphoric acid at 333 K were studied. The cluster structure parameters of the chemical network of epoxy-phenolic polymeric coating on a tin plate, obtained by thermal curing of precondensates of an oligomer mixture, were determined using the silver chloride sputtering method.Translated from Zhurnal Prikladnoi Khimii, Vol. 77, No. 8, 2004, pp. 1382–1388.Original Russian Text Copyright © 2004 by Krasovskii, Novikov, Filippov.     

[1,2]-Wittig rearrangement from chloromethyl ethers

The reaction of different chloromethyl ethers 1 with an excess of lithium powder and a catalytic amount of 4,4′-di-tert-butylbiphenyl (2.5 mol %) in THF at 0 °C leads to the corresponding α-lithiomethyl ether intermediates, through a chlorine-lithium exchange, which spontaneously undergo a clean [1,2]-Wittig rearrangement affording the expected homobenzylic alcohols 2. This is the first version of this rearrangement starting from easily available chloromethyl ethers.     

Peculiarities of tetrachloromethane vapor sorption by mesoporous γ-Al<Subscript>2</Subscript>O<Subscript>3</Subscript> templated at different stages of sol-gel process

The processes of adsorption-desorption of tetrachloromethane vapors by mesoporous -Al₂O₃ were investigated. Aluminum oxide was synthesized by the template method in the presence of micelles of cationic (cetylpyridinium chloride) and nonionic (Tween-85) surfactants added at various stages of sol-gel process. It was revealed that the shape of hysteresis loops depends on the structural peculiarities of the mesophase of template and gel-like boehmite. It was assumed that this effect is associated with the transformation of bottle-shaped mesopores into open cylindrical mesopores.Translated from Kolloidnyi Zhurnal, Vol. 66, No. 6, 2004, pp. 788–792.Original Russian Text Copyright © 2004 by Kuznetsova, Ratko.