Synthesis of N-aryl-1,5,3-dithiazepanes and N-aryl-1,5,3-dithiazocanes in the presence of samarium- and cobalt-containing catalysts

Efficient procedures were developed for the synthesis of N-aryl-1,5,3-dithiazepanes and N-aryl-1,5,3-dithiazocanes by cyclocondensation of anilines with formaldehyde and α,ω-dithiols (etane-1,2-dithiol and propane-1,3-dithiol), as well as by transamination of N-tert-butyl-1,5,3-dithiazepane or N-tert-butyl-1,5,3-dithiazocane with aromatic amines in the presence of samarium and cobalt complexes.     

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.     

Synthesis of α,ω-bis-1,5,3-dithiazepanes and their fungicidal properties

A procedure was developed for preparative synthesis of α,ω-bis-1,5,3-dithiazepanes by heterocyclization of aliphatic α,ω-diamines with N,N,N′,N′-tetramethylmethanediamine and 1,2-ethanedithiol. The fungicidal activity of 1,2-bis(1,5,3-dithiazepan-3-yl)ethane and 3,3′-(3,6-dioxaoctane-1,8-diyl)bis-1,5,3-dithiazepane toward microscopic fungi affecting agricultural plants was studied.     

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.     

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.     

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.     

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.     

Perhydro dioxazepines-1,5,3 : Methode generale de synthese

Perhydrodioxazepines-1,5,3 are obtained by reacting a primary amine with a 1,2-diol and paraformaldehyde.     

Efficient synthesis of 3-aryl(hetaryl)-1,5,3-dioxazepanes involving catalysts containing Sm and Co

Efficient synthetic procedure was developed for 3-aryl(hetaryl)-1,5,3-dioxazepanes consisting in the transamination of 3-tert-butyl-1,5,3-dioxazepane with arylamines and also by the reaction of 1,2-ethanediol with N,N-bis(methoxymethyl)aryl(hetaryl)amines in the presence of catalytic amounts of Sm and Co compounds.     

Мulticomponent Reactions of NH4Cl,CH2O and SH‐acids in Water as Effective Synthesis of Biologically Active Heterocycles

Multicomponent reactions of ammonium chloride in water with formaldehyde and SH‐acids (H₂S, ethane‐1,2‐dithiol) proceed with selective formation of such heterocycles as 3,7‐dithia‐1,5‐diazabicyclo[3.3.1nonane, 3‐(1,5,3‐dithiazepan‐3‐ylmethyl)‐1,5,3‐dithiazepanе and 1,6‐bis‐(1,5,3‐dithiazepan‐3‐yl)‐2,5‐disulphanylhexane. With participation of 1,3‐propanedithiol, this reaction leads to the formation of three‐dimensional hetero(S,N)‐chain polymer. The antifungal activity of 3,7‐dithia‐1,5‐diazabicyclo[3.3.1]nonane against microscopic fungi Bipolaris sorokiniana, Fusarium oxysporum and Aspergillus niger and same for 1,6‐bis‐(1,5,3‐dithiazepan‐3‐yl)‐2,5‐disulphanylhexane against Botrytis cinerea and Rhizoctonia solani was evaluated.     

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.     

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.     

A new method for the synthesis of α,ω-bis-1,5,3-dithiazepinanes using SmCl3·6H2O as the catalyst

An efficient method for the selective synthesis of previously unknown α,ω-bis-1,5,3-dithiazepinanes based on the transamination reaction of N-tert-butyl-1,5,3-dithiazepinane and recyclization reaction of 1-oxa-3,6-dithiacycloheptane with aliphatic diamines in the presence of SmCl₃·6H₂O as the catalyst, has been developed.     

Multicomponent cyclothiomethylation of phenylenediamines and 4,4'-diaminodiphenyls with formaldehyde and 1,2-ethanedithiol

One-pot synthesis of bis-1,5,3-dithiazepanes by cyclothiomethylation of o-phenylenediamine, 4,4'-diaminodiphenyl, 4,4'-diaminodiphenyl oxide, and 4,4'-diaminodiphenylmethane with formaldehyde and 1,2- ethanedithiol was performed. Sorption properties of the newly synthesized bis[4-(1,5,3-dithiazepan-3-yl)-phenyl] oxide were investigated by the batch technique. High efficiency of the recovery of palladium(II) with this reagent from hydrochloric acid solutions at room temperature was shown.     

Synthesis of 4-trihalomethyl-2-oxobenz-1,5,3-oxathiazepines and 2-oxo-4-trichloromethylbenz-1,5,3-dithiazepine and their conversion to 2-trihalomethyl-2-isocyanatobenz-1,3-oxathiolanes and 2-isocyanato-2-trichloromethylbenz-1,3-dithiolane

The reaction of perhaloethyl isocyanates with o-mercaptophenol and o-dimercaptobenzene gave 4-trihalomethyl-2-oxobenz-1,5,3-oxathiazepines and 2-oxo-4-trichloromethylbenz-1,5,3-dithiazepine, which at 100–110°C undergo contraction of the heteroring and are converted to the corresponding 2-trihalomethyl-2-isocyanato-1, 3-oxathiolanes and a dithiolane.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 11, pp. 1472–1474, November, 1993.We thank the State Committee for Problems of Science and New Technology of Ukraine for financial support of this research.     

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 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 N-substituted tetrapropargylamines by catalytic aminomethylation of α,ω-diacetylenes

Chemistry of Heterocyclic Compounds - A catalytic method was developed for the synthesis of N-substituted tetrapropargylamines by reactions of α,ω-diacetylenes with 1,5,3-dioxazepanes,...     

Structure of 2H-3,4-dihydro-3-phenyl-3-oxo-1,5,3-benzodioxaphosphepine

Conclusions The seven-membered heterocycle in 2H-3,4-dihydro-3-phenyl-3-oxo-1,5,3-benzodioxaphosphepine was found to have twist conformation by x-ray diffraction structural analysis.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskya, No. 5, pp. 1150–1152, April, 1989.     

An efficient synthesis of 3-alkyl-1,5,3-dioxazepanes and their use as electrophiles in double-Mannich reactions

An efficient synthesis of 3-alkyl 1,5,3-dioxazepanes was developed for subsequent use in double-Mannich reactions with a variety of carbon-based nucleophiles. It was found that addition of methyltrichlorosilane to the dioxazepane led to a long-lasting reactive species that reacted rapidly with acid-sensitive ketones and β-ketoesters to afford azabicyclo[3.3.1]nonanes in good yield.