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.     

Dehydrogenation of 1-aryl(hetaryl)-1,2,3,4-tetrahydro-9<Emphasis Type="Italic">H</Emphasis>-β-carboline-3-carboxylic acids and their esters with dimethyl sulfoxide

Oxidative dehydrogenation of 1-aryl(hetaryl)-1,2,3,4-tetrahydro-9Н-β-carboline-3-carboxylic acids derivatives with dimethyl sulfoxide leads to the formation of 1-aryl(hetaryl)-9Н-β-carbolines. Simultaneously with the dehydrogenation decarboxylation occurs. At the oxidation with dimethyl sulfoxide of methyl 1-aryl (hetaryl)-1,2,3,4-tetrahydro-9Н-β-carboline-3-carboxylicates methyl 1-aryl(hetaryl)-9Н-β-carboline-3-carboxylates formed whose hydrolysis afforded the corresponding 1-aryl(hetaryl)-9Н-β-carboline-3-carboxylic acids.     

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.     

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.     

Hydrazines in the synthesis of N-substituted 1,5,3-dithiazocan-3-amines catalyzed by Ti and Cu compounds

Efficient preparation method was developed for N-aryl(benzyl, alkyl)-1,5,3-dithiazocan-3-amines consisting in the transamination of 3-tert-butyl-1,5,3-dithiazocane with aryl(benzyl)hydrazines, and also in the reaction of N ¹,N ¹,N ⁷,N ⁷-tetramethyl-2,6-dithiaheptane-1,7-diamine with aryl(benzyl, alkyl)hydrazines in the presence of catalytic amounts of Ti and Cu compounds.     

Plant coumarins: XI. Cross coupling reactions with 2-(tosyl)oreoselone

The reaction of a linearly fused furocoumarin, oreoselone, with p-toluenesulfonyl chloride gave 2-tosyloreoselone which showed a high reactivity in palladium-catalyzed cross-coupling reactions with formation of a new carbon-carbon bond. 2-Tosyloreoselone reacted with terminal alkynes in the presence of Pd(PPh₃)₂Cl₂ to give the corresponding 2-alkynylfuro[3,2-g]chromen-3-ones. 2-Aryl(hetaryl)alkynyloreoselones were obtained in high yield directly by palladium-catalyzed reaction of oreoselone with tosyl chloride and aryl(hetaryl)acetylenes. The reaction of 2-tosyloreoselone with aryl(hetaryl)boronic acids in the presence of palladium complexes with uni- and bidentate ligands, tetrabutylammonium bromide, and a base afforded 2-aryl(hetaryl)-substituted oreoselones. 2-Vinyloreoselone was synthesized from 2-tosyloreoselone and potassium trifluoro(vinyl)borate.     

Stable nitroxyl radicals with triple bonds: 4-acetylenyl-3-imidazoline-3-oxide-1-oxyls

Cross-coupling reaction of 1-hydroxy-2,2,5,5-tetramethyl-4-[2-(p-iodophenyl)vinyl]-3-imidazoline-3-oxide with copper(I) salts of 1-aryl(hetaryl)alkynes leads to the corresponding 2,2,5,5-tetramethyl-4-[2-(p-aryl(hetaryl)ethynylphenyl)vinyl]-3-imidazoline-3-oxide-1-oxyls in high yields.     

Chemistry of iminofurans: IX. Synthesis and cyclization of (2<Emphasis Type="Italic">Z</Emphasis>)-2-{(2<Emphasis Type="Italic">Z</Emphasis>)-2-[2-(3-R-adamantan-1-yl)-2-oxoethylidene]hydrazinyl}-4-(het)aryl-4-oxobut-2-enoic acids

1-(3-R-adamantan-1-yl)-2-[(triphenyl-λ⁵-phosphanylidene)hydrazinylidene]ethanone reacted with 4-aryl(hetaryl)-2,4-dioxobutanoic acids to give 2-{2-[2-(3-R-adamantan-1-yl)-2-oxoethylidene]hydrazinyl}-4-aryl(hetaryl)-4-oxobut-2-enoic acids which were shown to exist in solution as mixtures of Z- and E-isomeric enehydrazine tautomers. The products underwent cyclization to 3-{[2-(3-R-adamantan-1-yl)-2-oxoethylidene]- hydrazinylidene}-5-aryl(hetaryl)furan-2(3H)-ones.     

Chemistry of iminofurans: X. Synthesis and hydrolysis of 5-aryl(hetaryl)-2-[(4,5,6,7-tetrahydro-1-benzothiophen-2-yl)imino]furan-3(2<Emphasis Type="Italic">H</Emphasis>)-ones

5-Aryl(hetaryl)furan-2,3-diones reacted with N-(triphenyl-λ⁵-phosphanylidene)-4,5,6,7-tetrahydro-1-benzothiophen-2-amines to give 5-aryl(hetaryl)-2-[(4,5,6,7-tetrahydro-1-benzothiophen-2-yl)imino]furan-3(2H)-ones whose acid hydrolysis afforded 4-aryl(hetaryl)-2-hydroxy-4-oxo-N-(4,5,6,7-tetrahydro-1-benzothiophen- 2-yl)but-2-enamides.     

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.     

First acetylenic derivatives of stable 3-imidazoline nitroxides

The Stephens-Castro reaction of copper(I) salts of 1-aryl(hetaryl)alkynes with 2,2,5,5-tetramethyl-4-[2-(4-iodophenyl)-vinyl]imidazoline-3-oxide-1-ol proved to be a general method for the preparation of 2,2,5,5-tetramethyl-4-[2-(p-aryl(hetaryl)ethynylphenyl)]vinyl-3-imidazoline-3-oxide-1-oxyles.     

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.     

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.     

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.     

Reactions of 1-amino-2-nitroguanidine with 2-aryl(hetaryl)-1-nitro-1-ethoxycarbonyl(benzoyl)ethenes

Reactions of 1-amino-2-nitroguanidine with 2-aryl(hetaryl)-1-nitro-1-ethoxycarbonyl(benzoyl)-ethenes proceed via initial formation the aza-Michael product, are accompanied by liberation of nitroacetic ester (or nitroacetophenone), and result in N-aryl(hetaryl)methylidene-N-(2-nitroguanidino)amines.     

One-pot assembly of 4-methylene-3-oxa-1-azabicyclo[3.1.0]hexanes from alkyl aryl(hetaryl) ketoximes, acetylene, and aliphatic ketones: a new three-component reaction

A new three-component reaction between alkyl aryl(hetaryl)ketoximes, acetylene, and aliphatic ketones in the superbasic systems KOH/DMSO and LiOH/CsF/DMSO (70-90 °C, initial acetylene pressure 13-15 atm, 5-60 min) affords novel 4-methylene-3-oxa-1-azabicyclo[3.1.0]hexanes in yields of up to 75%. Using KOH/DMSO, the side products of the reaction are O-vinylketoximes and 2-aryl(hetaryl)pyrroles, while with LiOH/CsF/DMSO, the reaction proves to be selective, only minor amounts of the corresponding alkyl aryl(hetaryl) ketones being detectable.     

Efficient one-pot method for the synthesis of bis-propargylamines by the reaction of terminal acetylenes with 1,5,3-dioxazepanes catalyzed by cоpper chloride

An efficient method for the synthesis of N-substituted bis-propargylamines and bis(alkadiynyl)amines was developed. The method consists of the CuCl-catalyzed aminomethylation of terminal acetylenes and α,ω-diacetylenes with N-substituted 1,5,3-dioxazepanes.     

New Efficient Synthesis of Methyl Trans-2-Aryl (or Hetaryl)-1-Benzamidocyclopropancarboxylates

Methyl trans-2-aryl(or hetaryl)-1-benzamidocyclopropancarboxylates can be easily obtained by thermal decomposition of trans-4-aryl(or hetaryl)-3-benzamido-3-carbomethoxy-Δ¹-pyrazolines synthesized by 1,3-dipolar cycloaddition of diazomethane with methyl E-3-aryl(or hetaryl)-2-benzamido-2-propenoates.