G. R. Khabibullina

Multicomponent reactions of amines with aldehydes and H2S as efficient route to heterocycles and thioaza macrocycles

Here we provide new experimental results on multicomponent reactions of amines with aldehydes and H2S in the directed synthesis of functionally-substituted 1,3-thiazetidines, 1,3,5-dithiazinanes, 1,3,5-thiadiazinanes, 1,5-dithia-3,7-diazacyclooctanes, and thioaza macrocycles. X-ray analysis gave insight into the structure of the synthesized compounds. New kinds of multicomponent reactions (MCR) have been discovered and characterized.

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.

Sorption Properties of the Complex-Forming Sorbent Bis-1,3,5-dithiazinanee-5-yl-ethane with respect to Palladium(II), Silver(I), and Mercury(II)

Sorption properties of the weakly basic complex-forming sorbent bis-1,3,5-dithiazinane-5-yl-ethane with respect to Pd(II), Ag(I), and Hg(II) were studied. The sorbent was prepared from ethylenediamine, formic aldehyde, and H2S by a single-reactor procedure.

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 N- and N,N′-coordinated derivatives of 3,7-dithia-1,5-diazabicyclo[3.3.0]octanes and their fungicidal activity

Possibility of obtaining water-soluble N- and N,N′-coordinated adducts by reacting 3,7-dithia-1,5-diazabicyclo[3.3.0]octane with methyl iodide and Brønsted (HCl, HBr) and Lewis (AlCl3) acids was examined. The fungicidal activity of 3,7-dithia-1,5-diazabicyclo[3.3.0]octane and its water-soluble adducts with hydrobromide and methyl iodide against a number of microscopic fungi affecting cultivated plants and various materials was studied.

One-pot synthesis and fungicidal activity of 2-(1,5,3-dithiazepan-3-yl)ethanol and N,N′-bis(2-hydroxyethyl)tetrathiadiazacycloalkanes

Synthesis of 2-(1,5,3-dithiazepan-3-yl)ethanol and N,N′-bis(2-hydroxyethyl)tetrathiadiazacycloalkanes was performed by multicomponent condensation of monoethanolamine with formaldehyde and SH-acids (1,2-ethane, 1,3-propane-, 1,4-butane-, 1,5-pentane-, and 1,6-hexanedithiols). The resulting S,N-containing heterocycles and macrocycles possess fungicidal properties relative to microscopic fungi, plant pathogens.

A green synthesis in water of novel (1,5,3-dithiazepan-3-yl)alkanoic acids by the multicomponent reaction of amino acids, \hbox {CH}_{2}O, and 1,2-ethanedithiol

A library of new (1,5,3-dithiazepan-3-yl)alkanoic acids was prepared by the multicomponent cyclocondensation of amino acids, formaldehyde, and 1,2-ethanedithiol in water at room temperature for 1 to 5 h in high yields. This green procedure offers several advantages such as an operational simplicity, no catalyst, and no production of hazardous materials.

Intermolecular interactions and chiral crystallization effects in (1,5,3-dithiazepan-3-yl)-alkanoic acids

Crystals of (1,5,3-dithiazepan-3-yl)-alkanoic acids with achiral and chiral amino acid moieties have been obtained, and their structures were studied using a single crystal X-ray technique. Simple crystal systems, namely monoclinic, triclinic, and orthorhombic, were revealed in a series of the studied compounds. The reference 1,5,3-dithiazepan-3-ol forms head-to-head cyclic dimeric associates R22(6) via strong O–H⋯N intermolecular hydrogen bonds. The achiral 1,5,3-dithiazepanes form head-to-head cyclic dimers R22(8) between two carboxylic groups, whereas the co-crystals involve solvent molecules to constitute dimeric pairs R33(11) and R22(8) through O⋯H and N⋯H hydrogen bonds. These dimers further contribute to the aggregation of layers and stacks due to diverse H⋯H and S⋯H contacts. The chiral dithiazepanes form head-to-tail R12(6), R22(7), and R22(8) cyclic dimers between the carboxylic group of one molecule and the dithiazepane moiety of the other one through H⋯H, S⋯H, and O⋯H intermolecular contacts. Hirshfeld analysis has shown that S⋯H (9.2–19.8%) and O⋯H (5.4–18.2%) intermolecular hydrogen bonds as well as weak H⋯H contacts (40.2–64.0%) are predominant in all the compounds to form crystal packing.

Synthesis and separation of stereoisomeric 2,4,6,8-tetrasubstituted 3,7-dithia-1,5-diazabicyclo[3.3.0]octanes

Heterocyclization of hydrazine with aldehydes R-CHO (R = Me, Et, Prn, Bun, n-C5H11, Ph, 4-MeOC6H4, 3-Py) and H2S leads to stereoisomeric 2,4,6,8-tetrasubstituted 3,7-dithia-1,5-diazabicyclo[3.3.0]octanes, which were separated by column chromatography. The trans-transoid-trans-configuration of tetramethyl(-ethyl,-propyl)-3,7-dithia-1,5-diazabicyclo-[3.3.0]octanes was inferred from the X-ray diffraction and 1H and 13C NMR spectroscopic data.