Crystal and molecular structures of 2,10-diacetoxy-13-thiabicyclo[7.3.1]-cis-tridec-5-ene and 2,9-dichloro-13-thiabicyclo[8.2.1]-cis-tridec-5-ene sulfoxide

The crystal and molecular structures of 2,10-diacetoxy-13-thiabicyclo[7.3.1]-cis-tridec-5-ene and 2,9-dichloro-13-thiablcyclo[8.2.1]-cis-tridec-5-ene sulfoxide were established. The conformations of the molecules are such that the unshared pairs of electrons of the sulfur atoms are directed to the carboncarbon double bonds of their molecules. It was observed that there are stereochemical conditions for transannular transformations under the influence of polarized molecules and cations.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 12, pp. 1628–1632, December, 1977.     

Synthesis, structure and reactivity of binuclear metal-metal bonded molybdenum(V) and tungsten(V) thioselenohalides: Molecular structure of Mo2(μ-S2)2Cl6(SeCl2)2 and W2(μ-S2)2Cl6(SeCl2)2

Thioselenohalide complexes Mo₂(μ-S₂)₂Cl₆(SeCl₂)₂ (I), Mo₂(μ-S₂)₂Br₆(SeBr₂)₂ (II), and W₂(μ-S₂)₂Br₆(SeBr₂)₂ (III) were synthesized by the reactions of corresponding metal halides or carbonyls or molybdenum metal with excesses of S₂ X ₂+Se₂ X ₂ mixtures. The complex W₂(μ-S₂)₂Cl₆(SeCl₂)₂ (IV) was obtained by an exchange reaction between (III) and excess of Se₂Cl₂. Coordination of the neutral SeX ₂ ligands to thiohalidesM ₂(μ-S₂)₂ X ₆ results in higher thermal stability, and suggests the possibility to synthesize SeX ₂ complexes of the unstable parent tungsten thiohalides. An unusual oxidative addition reaction of (I) was detected: {fx27-1} Both (I) and (IV) were characterized by X-ray crystal structure analysis. They are isostructural and form discrete molecules. Bridging S ₂ ^2? ligands are coordinated perpendicularly to the metal-metal bond;d(M?M)=2.8066 Å and 2.793 Å for I and IV, respectively. Nonequivalence of chlorine atoms which are bound to the metal atom, relate to nonequivalence of halogen atoms in the complexesM ₂(μ?S₂)₂ X ₈ ^2? . Chlorine atomstrans to SeCl₂ ligands form short bonds with the metal; the corresponding³⁵Cl NQR frequency is increased. The selenium dichloride ligand is ambidentate. The selenium atom binds as a donor to the metal and as an acceptor to two chlorine atoms which are also bound covalently to the same metal atom.     

Production of new lagochilin derivatives

The tetrahydric alcohol Lgochilin belongs to the 9,13-epoxylabdane series of diterpenoids. It is produced by many species of plants of the Lagochilus genus and can be used as the starting material for the synthesis of new compounds with a broad spectrum of physiological action [1, 2]. Many lagochilin derivatives possess hemostatic (3, 4) and antiviral properties. Lagochilin derivatives with aromatic hydroxaldehydes and naphthaldehydes have been synthesized, and the cytotoxic effects of the compounds synthesized in cell cultures have been studied.Tashkent State University, (fax (3712) 46 24. 42. Translated from Khimiya Prirodnykh Soedinenii, No. 1, pp. 86–88, January–February, 1995. Original article submitted October 17, 1994.