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.     

Twist‐chair conformation of the tetraoxepane ring remains unchanged in tetraoxaspirododecane diamines

A detailed structural analysis has been performed for N,N′‐bis(4‐chlorophenyl)‐7,8,11,12‐tetraoxaspiro[5.6]dodecane‐9,10‐diamine, C₂₀H₂₂Cl₂N₂O₄, (I), N,N′‐bis(2‐fluorophenyl)‐7,8,11,12‐tetraoxaspiro[5.6]dodecane‐9,10‐diamine, C₂₀H₂₂F₂N₂O₄, (II), and N,N′‐bis(4‐fluorophenyl)‐7,8,11,12‐tetraoxaspiro[5.6]dodecane‐9,10‐diamine, C₂₀H₂₂F₂N₂O₄, (III). The seven‐membered ring with two peroxide groups adopts a twist‐chair conformation in all three compounds. The lengths of the C—N and O—O bonds are slightly shorter than the average statistical values found in the literature for azepanes and 1,2,4,5‐tetraoxepanes. The geometry analysis of compounds (I)–(III), the topological analysis of the electron density at the (3, ?1) bond critical points within Bader's quantum theory of `Atoms in molecules' (QTAIM) and NBO (natural bond orbital) analysis at the B3LYP/6‐31G(d,2p) level of theory showed that there are n_O→σ*(C—O), n_N→σ*(C—O) and n_O→σ*(C—N) stereoelectronic effects. The molecules of compounds (I) and (III) are packed in the crystals as zigzag chains due to strong N—H…O and C—H…O hydrogen‐bond interactions, whereas the molecules of compound (II) form chains in the crystals bound by N—H…O, C—H…π and C—H…O contacts. All these data show that halogen atoms and their positions have a minimal effect on the geometric parameters, stereoelectronic effects and crystal packing of compounds (I)–(III), so that the twist‐chair conformation of the tetraoxepane ring remains unchanged.     

Efficient Synthesis of N-Aryl-substituted Nonathiatriaza-(1,4)-hexabenzocyclotetracosaphanes

Russian Journal of Organic Chemistry - 6,14,22-Triaryl-2,4,8,10,12,16,18,20,24-nonathia-6,14,22-triaza-1,3,9,11,17,19(1,4)-hexabenzocyclotetracosaphanes are synthesized in high yield and...     

A new synthesis method of N-substituted spiro terpene aza-diperoxides

Chemistry of Heterocyclic Compounds - An efficient method has been developed for the synthesis of new spiro terpene aza-diperoxides by heterocyclization of bishydroperoxides with...     

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,molecular structure,conformation and biological activity of Ad-substituted N-aryl-tetraoxaspiroalkanes

An efficient method has been developed for the synthesis of 7′-arylspiro{adamantane-[2,3′]-(1′,2′,4′,5′,7′-tetraoxazocanes)} by the ring transformation reaction of spiro{adamantane-[2,3’]-(1′,2′,4′,5′,7′-pentaoxacane)} with arylamines in the presence of Sm(NO₃)₃·6H₂O as the catalyst. NMR signals of the synthesized compounds were assigned considering the conformation dynamics of the tetraoxazocane ring with two rigid peroxide bonds. The structures of some of the compounds were studied by X-ray diffraction. The thermal stability of single crystal was determined by DSC method. Compounds 7′-(2-methylphenyl)spiro{adamantane-[2,3′]-(1′,2′,4′,5′,7′-tetraoxazocane)} and 7′-(4-fluorophenyl)spiro{adamantane-[2,3′]-(1′,2′,4′,5′,7′-tetraoxazocane)} exhibited cytotoxicity towards cancer cells.