Synthesis of 3-hetaryl-1,5,3-dithiazepanes and 3-hetaryl-1,5,3-dithiazocanes in the presence of catalysts based on transition metals

Efficient procedure was developed for 3-hetaryl-1,5,3-dithiazepanes and 3-hetaryl-1,5,3-dithiazocanes preparation from hetarylamines, N,N,N′,N′-tetramethylmethanediamine, and α,ω-alkanedithiols (ethane-1,2-dithiol, propane-1,3-dithiol), and also by the reaction of the latter with N,N-bis(methoxymethyl)hetarylamines in the presence of catalytic quantities of transition metals salts.     

Catalytic Synthesis of N-Aryl-1,5,3-dithiazocanes

Russian Journal of Organic Chemistry - An efficient procedure has been developed for the synthesis of N-aryl-1,5,3-dithiazocanes and 1,1′-biphenylenebis(1,5,3-dithiazocanes) by...     

Synthesis and Fungicidal Activity of Bis-1,5,3-dithiazepanes and Crown-Like Macroheterocycles

Russian Journal of General Chemistry - An efficient method was developed for the synthesis of bis-1,5,3-dithiazepanes and crown-like N-cycloalkyl-1,11-dioxa-4,8-dithia-6-azacyclotridecanes by...     

Synthesis of bis-1,5,3-dithiazepanes on the basis of aromatic diamines

Russian Journal of Organic Chemistry - A procedure has been developed for the synthesis of N,N′-disubstituted bis-1,5,3-dithiazepanes by samarium-catalyzed recyclization of...     

Synthesis of N-(1,5,3-dithiazepan-3-yl)- and N-(1,5,3-dithiazocan-3-yl)amides in the presence of lanthanide catalysts

A new method was developed for preparation of N-(1,5,3-dithiazepan-5-yl)- and N-(1,5,3-dithiazocan-5-yl)amides by transamination of N-tert-butyl-1,5,3-dithiazepane and N-tert-butyl-1,5,3-dithiazocane, and also by recyclization of 1-oxa-3,6-dithiacycloheptane and 1-oxa-3,7-dithiacyclooctane with carboxylic acids hydrazides in the presence of catalysts based on rare earth elements.     

Hydrazines in the synthesis of 1,5,3-dithiazepane and 1,5,3-dithiazocane derivatives in the presence of catalysts under the action of d- and f-elements

A method of synthesis was developed for 1,5,3-dithiazepan(dithiazocan)-3-ylamines and 3,3′-bi-1,5,3-dithiazepane(dithiazocane) by hydrazines cyclocondensation with formaldehyde and α,ω-alkanedithiols (1,2-ethanedithiol, 1,3-propanedithiol) involving catalysts based on d- and f-elements.     

Novel 1,5,3-dithiazepanes: three-component synthesis, stereochemistry, and fungicidal activity

Three-component heterocyclization of hydrazine with formaldehyde and ethane-1,2-dithiol gave previously unknown 3,3′-bi(1,5,3-dithiazepane). Its stereochemistry was determined by X-ray diffraction. The reaction with higher aliphatic aldehydes RCHO (R = Me, Et, Prⁿ, and Bun) yielded 2,4-dialkyl-3-alkylideneamino-1,5,3-dithiazepanes. The stereochemistry of the latter was determined by ¹H and ¹³C NMR spectroscopy and confirmed by quantum chemical calculations. Heterocyclizations of phenylhydrazine and benzylhydrazine with ethane-1,2-dithiol gave 3-amino-1,5,3-dithiazepanes only with CH₂O and MeCHO as the aldehyde component. 3,3′-Bi(1,5,3-dithiazepane) and its N-adduct with MeI were found to exhibit fungicidal activity against microscopic fungi.     

One-pot synthesis of bis-1,5,3-dithiazepanes from ethane-1,2-dithiol, formaldehyde, and ammonium salts

An efficient one-pot procedure has been developed for the synthesis of bis-1,5,3-dithiazepanes by reaction of ethane-1,2-dithiol with formaldehyde and ammonium salts. According to the X-ray diffraction data, the heterorings in 3,3′-[ethane-1,2-diylbis(sulfanediylmethanediyl)]bis(1,5,3-dithiazepane) in crystal adopt a chair conformation with axial orientation of the substituent on the nitrogen atom.     

Efficient synthesis of bis(1,5,3-dithiazepanes). Sorption of palladium(II) from nitric acid solutions

Bis(1,5,3-dithiazepanes) have been synthesized via cyclocondensation of aliphatic α,ω-diamines and hydrazine with formaldehyde and ethane-1,2-dithiol. Palladium(II) sorption with bis(1,5,3-dithiazepanes) from nitric acid solutions has been studied via a static method. Bis(1,5,3-dithiazepanes) efficiently extract palladium(II) from 0.1?4 mol/L nitric acid solutions at room temperature.     

One-pot synthesis of bis-1,5,3-dithiazepanes and their sorption properties toward silver(I) and palladium(II)

The possibility of one-pot synthesis of bis-1,5,3-dithiazepanes by multicomponent condensation of amines (NH₄Cl, hydrazine, and 1,2-ethylenediamine) with formaldehyde and 1,2-ethanedithiol was described. Their sorption properties relative to Ag(I) and Pd(II) were studied by a static method. It was shown that at room temperature bis-1,5,3-dithiazepanes recovered with high efficiency silver(I) and palladium(II) from nitrate solutions and hydrochloric acid solutions, respectively.     

Synthesis of methylmercaptane in the presence of base catalysts

Interaction of methanol with H₂S has been studied at 360–500°C in the presence of Al₂O₃ promoted by alkaline metal compounds. As found, catalysts, obtained via promoting Al₂O₃ by carbonate, and potassium or sodium hydroxide, are more basic in relation to tung-state samples. The total catalytic activity increased, while the selectivity toward methylmercaptane decreased with increasing surface basicity.

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360–500°C Al₂O₃, . , , Al₂O₃ , . - .

     

Synthesis of polyolefin composition in the presence of supported catalysts

Polyolefins are basic materials in the plastics. Their application is limited by their low thermostability, adhesion, hardness and other physico-mechanical properties. The following treatments are known to improve and modify polyolefin properties: the incorporation of inorganic or organic fillers with a greater hardness and rigidity into the polyolefin matrix, the grafting of functional groups to polyolefins, and crosslinking with the formation of a network structure in the polyolefin matrix. In the case of polymers and inorganic materials, the activation of their surface by the functionalizing and fixing of transition metals allows one to perform polymerization of monomers on a surface to obtain a polymer–polymer composites and a highly filled polymer–inorganic composites.     

Synthesis of 4-methylthiazole in the presence of acid-base catalysts

The formation of 4-methylthiazole from methylisopropylidenimine and SO₂ on acid-base catalysts has been studied. The most active catalysts are those containing an acid-base pair: a weak Lewis site and a strong basic site. The catalysts containing only proton-donating sites are low-active.     

Synthesis and thermal decomposition of cobalt-containing oligosilanes

Oligo(phenylcobaltcarbonylsilane) was prepared from oligo(phenylsilane) and dicobalt octacarbonyl. The reaction proceeds with elimination of H₂ and CO and insertion of cobalt carbonyl fragments into the silicone backbone of oligosilane. Oligosilane containing cobalt carbonyl groups in side organic substituents was obtained from oligolmethyl(phenylethynyl)Isilane and CO₂(CO)₈. The reaction of 1,2-bis(phenylethyny1)tetramethyldisilane with Co₂(CO)₈ proceeds with the sequential attachment of cobalt carbonyl fragments to ethynyl groups to form disilane derivatives [²-CCPhCo₂(CO)₆] Thermal decomposition of cobalt-containing oligosilanes affords a mixture of paramagnets and ferromagnets.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya. No. 10, pp. 2561–2567, October, 1996.     

Synthesis of diethyl ether in presence of zeolite catalysts

Conclusions Ethanol, containing 10–30 mole% of C₂H₅I, is converted mainly to diethyl ether in the presence of zeolites NaX, NaY, HY, and HM, at a temperature of 160–200° and atmospheric pressure. Intense dehydration of the ethanol to ethylene occurs without the C₂H₅I.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 1, pp. 196–199, January, 1979.     

均相催化剂催化合成碳酸亚丙酯

分别就单组为催化剂和双组分催化剂对二氧化碳与环氧丙烷合成碳酸亚丙酯的催化活性进行了研究。实验结果表明，在单组分催化体系中，相转移催化剂，如十六烷基三甲基漠化按、四丁基演化铵对上述酯化反应具有较高的催化活性此外，盐酸羟胺、三苯基磷也有一定的催化活性；在双组分催化体系中，KI／PEG（聚乙二醇）体系具有很高的催化活性，能在较短时间内、较低的压力下高产率地得到碳酸亚丙酯，而某些金属盐、有机碱、季接盐的适当红合，也能有效地催化该反应。     

Synthesis of amino sulfides in the presence of rare-earth and transition metal catalysts

Efficient procedures have been developed for the synthesis of amino sulfides by aminomethylation of thiols with higher geminal diamines, thiomethylation of secondary amines with N,N-dimethylaminomethyl sulfides, and decyclization of 1,3,6-oxadithiepane or N-tert-butyl-1,5,3-dithiazepane with secondary amines in the presence of rare-earth and transition metals.     

Synthesis of nitriles from acetonitrile and methanol in the presence of oxide catalysts

The promoting effect of potassium included in Cr/MgO catalysts for the synthesis of nitriles from acetonitrile and methanol was found. The 5% Cr-0.5% K/MgO catalyst exhibited the highest activity in the synthesis of nitriles. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 8, pp. 1540–1542, August, 1997.