Asymmetrical oxidation of menthone dithiolane

Asymmetrical oxidation was performed of menthone dithiolane obtained in 95–98% yield by condensation of menthone with 1,2-ethanedithiol in the presence of boron trifluoride etherate. 6-Isopropyl-9-methyl-1,4-dithiaspiro[4,5]decane-1,4-dioxide (yield 5–55%) and 6-isopropyl-9-methyl-1,4-dithiaspiro[4,5]-decane-1,1,4-trioxide (yield 65–70%) were synthesized. Chemical structures of compounds obtained were proved by XRD analysis, NMR and IR spectroscopy.     

Photochemistry of spiropyrans of the dithiolane series with polycondensed chromene fragments

It has been shown on the basis of determinations of the values of the quantum yields of the photocoloration of spiropyrans of the 1,3-dithiolane and benzo1,3-dithiolane series that the annelation of a benzene ring in the chromene part of the molecule results in an increase in the efficiency of photocoloration and an increase in the stability of the merocyanine forms of the compounds investigated.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 11, pp. 2504–2510, November, 1989.     

Synthesis and magnetic properties of new mono- and binuclear iron complexes with salicyloylhydrazono dithiolane ligand

We report here experimental evidence for the formation in the solid state of a new binuclear Fe (III) 2(mu-OMe) 2(HL) 4 complex (H 2L is 2-salicyloylhydrazono-1,3-dithiolane). The isostructural Mn (III) 2(mu-OMe) 2(HL) 4 complex has provided the strongest ferromagnetic interaction value (J approximately 20 cm (-1)) between Mn (III) ions to date. The new iron binuclear compound presented in this study shows antiferromagnetic intramolecular coupling, which agrees with the theoretical study that we previously proposed. During our synthetic work, we also observed an unexpected spontaneous reduction of the new Fe (III)(HL) 2Cl,S complex to the new Fe (II)(H 2L) 2Cl 2 high-spin mononuclear complex. This process has been checked by cyclo-voltammetry as well as pseudosteady voltammetry.     

Synthesis,stereochemistry and adsorption studies of new spiranes and polyspiranes containing 1,2‐dithiolane units

The synthesis and stereochemistry of a series of new cyclic disulfides containing (poly)spirane 1,2‐dithiolane units are reported. Also included is a study of the self‐assembled monolayers (SAMs) of these compounds on a gold surface. The characteristics of the resultant SAMs were determined by IR spectroscopy using molecular mechanics calculations.     

Palladium-catalyzed cyclization reactions of 2-vinylthiiranes with heterocumulenes. Regioselective and enantioselective formation of thiazolidine, oxathiolane, and dithiolane derivatives

The first palladium-catalyzed ring-expansion reaction of 2-vinylthiiranes with heterocumulenes to form sulfur-containing five-membered-ring heterocycles is described. This regioselective reaction requires 5 mol % of Pd(2)(dba)(3).CHCl(3) and 10 mol % of bidendate phosphine ligand (dppp, BINAP), at 50-80 degrees C, in THF. The reaction of 2-vinylthiiranes with carbodiimides, isocyanates, and ketenimines affords 1,3-thiazolidine derivatives, whereas the reaction with diphenylketene or isothiocyanates results in the formation of 1,3-oxathiolane or 1,3-dithiolane compounds in good to excellent isolated yields and in up to 78% ee.     

Synthesis and antimicrobial evaluation of some novel dithiolane,thiophene, coumarin,and 2-pyridone derivatives

Novel 2-cyano-N-[1-(naphtha-2-yl)ethylidene] acetohydrazide 1 was utilized as key intermediate for the synthesis of some new dithiolane, thiophene, coumarin, 2-pyridone, and other related products containing a hydrazide moiety. Newly synthesized compounds were characterized by elemental analyses and spectral data (IR, ¹H NMR and mass spectra). The antimicrobial activity of the synthesized compounds was evaluated.     

Selective immobilization of double stranded DNA on a gold surface through threading intercalation of a naphthalene diimide having dithiolane moieties

Newly synthesized naphthalene diimide 1 having two dithiolane moieties at its substituted termini bound to double stranded DNA by threading intercalation and the resulting complex was immobilized on the gold surface through a dithiolane-gold linkage as revealed by quartz crystal microbalance (QCM) experiments. DNA with 20-meric double stranded and 24-meric single stranded regions was indirectly immobilized on the gold electrode using this characteristic of 1. Hybridization efficiency was 92%, a value higher than 50% for a thiolated oligonucleotide under identical conditions. When this electrode was subjected to hybridization with a 124-meric target DNA in the presence of ferrocenylnaphthalene diimide (FND) as an electrochemical hybridization indicator, a large current increase was observed deriving from FND bound in the double stranded region newly formed between the probe and target DNA.     

A tandem reaction of 2-acetylmethylene-1,3-dithiolanes via fragmentation of the dithiolane ring in the presence of amines: a facile route to functionalized thioamides

A facile and efficient route to functionalized thioamides has been developed by a tandem reaction of 2-acetylmethylene-1,3-dithiolanes via fragmentation of the dithiolane ring upon heating and in the presence of an amine.     

Synthesis and Some Reactions of 2‐Acyl‐2‐alkyl‐1,3‐dithiolane 1,1‐Dioxides

The selective formation of optically active 2‐acyl‐2‐alkyl‐1,3‐dithiolane 1,1‐dioxides from the corresponding 2‐acyl‐2‐alkyl‐1,3‐dithiolane 1‐oxides, by reaction with OsO₄ and NMO in acetone, is reported. These compounds underwent stereoselective reactions at the carbonyl group of the acyl group with organometallic reagents. These reactions were completely regioselective, and no attack at either of the S‐atoms was observed, unlike similar reactions with the corresponding sulfoxides. The nature of the metal atom had a direct effect upon the configuration of the product alcohols.     

Effect of the nature of the heteroatoms in the spiro group on the structure of spiropyrans and an x-ray study of spiropyran of the dithiolane series C17H16O2S2

Conclusions We have carried out an x-ray diffraction study of tetramethylenespiro[1,3-dithiolane-2,7[7H]-furo[3,2-f]-[2H -1]-benzopyran], containing the three heteroatoms S, S, O in the spiro group. The orbital n-* interactions virtually do not affect the bond lengths in the spiro group of the molecule; therefore the C_spiro-O bond, which is ruptured upon photoexcitation, remains unlengthened in the ground state. The differences in the lengths of the chemically equivalent C_spiro-S bonds are due to electrostatic repulsions of the unshared electron pairs of the heteroatoms S and O, which have different relative orientation.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 7, pp. 1567–1569, July, 1988.     

Structure of sevedamine

From the combined chloroform-extracted material of the epigeal part ofKorolkowia sewerzowii Regel the new alkaloid sevedamine has been isolated, with mp 256–258°C (acetone) [α]_D +3.6° (c 1.25; ethanol), C₂₇H₄₅NO₃. On the basis of the results of a study of the UV, IR, PMR, and mass spectra of sevedamine and also performance of a transition to the known alkaloid korseverilinedione it has been established that sevedamine has the structure and configuration of 3β,6α,14α-trihydroxycevanine.     

Structure of subchrysin

A new sesquiterpene lactone having the structure 3-acetoxy-1-hydroxy-6, 7(H)-germacra-4,10(14), 11(13)-trien-6, 12-olide has been isolated fromArtemisia subchrysolepis Filat. and has been called subchrysin. Its stereochemistry has been established by x-ray structural analysis.Translated from Khimiya Prirodnykh Soedinenii, No. 2, pp. 176–180, March–April, 1998.