The mass spectral fragmentation of 1,4-butanediol

The behaviour of 1,4-butanediol under electron impact at 70 and 12.5 eV has been studied with the aid of high resolution mass spectra. Based on metastable ion decompositions and deuterium labelling, mechanisms are proposed for the formation of the abundant ions of this compound.     

Saturated heterocycles. Part 209. Synthesis of 1-cyclohexyl-substituted isoquinoline derivatives

In contrast with earlier literature data [7], both acrylic esters and acrylonitrile underwent Michael addition to l-methyl-3,4-dihydroisoquinolines 1-4 to yield the diesters 5-9 or the dinitrile 10 , respectively. Compounds 5-10 were converted by Claisen condensation to 1-[(3′-methoxycarbonyl- or 1-[(3′-ethoxycarbonyl-4′-oxo)-l'-cyclohexyl]-3,4-dihydroisoquinoline derivatives 11-16 . Several derivatives of 12 were prepared. The new compounds possess various pharmacological actions.     

Localization measure and maximum delocalization in molecular systems

A mathematically well-defined measure of localization is presented based on Mulliken's orbital populations. It is shown that this quantity equals 1 for core- and lone-pair orbitals, 2 for two-atomic bonds, 6 for benzene rings, etc., and it is applicable for delocalized canonical HF orbitals as well. The definition of this quantity is general in the sense that ab initio MOS with overlapping AO expansion, and semiempirical wave functions using the ZDO approximation as well, can be treated. The localization quantity is essentially “intrinsic,” i.e., no subdivision of the molecule is required. For N-electron wave functions, mean delocalization can be defined. This measure is not invariant to unitary transformations of the one-electron orbitals, characterizing in this way the localized or extended representation of the N-electron wave function. It can be proven, however, that for unitary transformed wave functions a maximum delocalization exists which depends only on the physical (N-electron) properties of the molecule. It is shown that inhomogeneous charge distribution can cause strong electron localization in molecular systems. The delocalization of the canonical Hartree–Fock orbitals, the Parr–Chen circulant orbitals, and the optimum delocalized orbitals is studied by numerical calculations in extended systems.     

On the maximal number of certain subgraphs inK r -free graphs

Given two graphsH andG, letH(G) denote the number of subgraphs ofG isomorphic toH. We prove that ifH is a bipartite graph with a one-factor, then for every triangle-free graphG withn verticesH(G) H(T ₂(n)), whereT ₂(n) denotes the complete bipartite graph ofn vertices whose colour classes are as equal as possible. We also prove that ifK is a completet-partite graph ofm vertices,r > t, n max(m, r – 1), then there exists a complete (r – 1)-partite graphG* withn vertices such thatK(G) K(G*) holds for everyK _r -free graphG withn vertices. In particular, in the class of allK _r -free graphs withn vertices the complete balanced (r – 1)-partite graphT _r–1(n) has the largest number of subgraphs isomorphic toK _t (t < r),C ₄,K _2,3. These generalize some theorems of Turán, Erdös and Sauer.Dedicated to Paul Turán on his 80th Birthday     

4,6-Thioanhydro-hexopyranosides,synthesis and chemical behaviour of methyl 2-0-p-toluenesulfonyl-4,6-thioanhydro-α-d-gulopyranoside

Methyl 4-0-benzoyl-6-bromo-6-deoxy-α-D-glucopyranoside ($\text{1}$, Figure 1) was converted, via the corresponding ditosylate $\text{2}$, into methyl 2,3-di-0-p-toluenesulfonyl-4-0-benzoyl-6-S-acetyl-6-thio-α-D-glucopyranoside ($\text{3}$) by a selective nucleophilic displacement of 6-bromo-group with thioacetate. Unexpectedly, on treating the compound $\text{3}$ with an excess of sodium methoxide in benzene-methanol (1:1) at room temperature, methyl 2-0-p-toluenesulfonyl-4,6-thioanhydro-α-D-gulopyranoside ($\text{4}$) was obtained in a yield of 84%. In order to determine the structure of the relatively unstable oily product $\text{4}$, some stable crystalline derivatives ($\text{5}$, $\text{6}$ and $\text{7}$) were prepared. Detailed analysis of the ¹H-NMR-spectra (200 MHz) of $\text{6}$ and $\text{7}$ gave the conclusive evidence for the structure of $\text{4}$ A self-imposing mechanism of the clean and smooth transformation of $\text{3}$ to $\text{4}$ is proposed, involving: a) formation of $\text{9}$ (Figure 2) as a crucial intermediate and b) a highly regioselective epoxide opening in $\text{9}$ (at C-4) by an intramolecular nucleophilic attack of the mercaptide anion from C-6.     

Cycloaddition reactions of 1.3-benzothiazines v synthesis of new tetracyclic ring systems

New tetracyclic derivatives (3a,$\text{b}$, 5, 8) similar to protoberberines, but containing a lactam structural element and other hetero atoms besides the bridge-head nitrogen in rings B and C, were prepared by cycloaddition of 6,7-dimethoxy-2H-1,3-benzothiazine (1a) with $\text{o}$-substituted aromatic carboxylic acid derivatives (2a,$\text{b}$, 4) and from 4- methyl-6,7-dimethoxy-2$\text{H}$-1,3-benzothiazine (1b) with 3.5-dinitrobenzoyl chloride.     

Synthesis and structural characterization of cobalt(II) and zinc(II) complexes with 2-(indazol-1-yl)-2-thiazoline (TnInA). X-ray characterization of [CoCl2(TnInA)2] · C2H6O and [(M)(TnInA)2(H2O)2](NO3)2 (M = Co, Zn)

Several complexes of 2-(indazol-1-yl)-2-thiazoline (TnInA) with the divalent ions Co and Zn have been synthesized by the direct combination of the ligand and the metal chloride or nitrate hydrated salts in ethanol. These complexes have been characterized by a variety of physical–chemical techniques. Moreover, the structures of [CoCl₂(TnInA)₂] · C₂H₆O (1) and [(M)(TnInA)₂(H₂O)₂](NO₃)₂ (M = Co, 3; Zn, 4) were determined by single-crystal X-ray diffraction. In all the complexes, the ligand TnInA bonds to the metal ion through the indazole and thiazoline nitrogen atoms. In complex 1 the environment around the cobalt ion may be described as a distorted octahedron with two TnInA ligands and two chlorine ligands. Compounds 3 and 4 are isostructural with a distorted octahedral geometry around the metal center, being linked to two water molecules and two TnInA ligands. However, in complex [ZnCl₂(TnInA)] (2) the zinc atom is four-coordinated with a probable tetrahedral environment with two chloro ligands and one TnInA ligand bonded to the metal ion.     

Synthesis and Circular Dichroism of Both Enantiomers of 2-deuterofluoroacetic acid ( Fluoro[2H1]acetic acid)

Sharpless epoxidation of (E)-1-(trimethylsilyl)[1-²H₁]oct-1-en-3-o1 ( 3a ) yielded (1S,2S,3S)- and (1R,2R,3R)-1-(trimethylsilyl)-1,2-epoxy[1-²H₁]octan-3-ols ( 4a and 4b , resp.) which were converted in three steps into (S)- and (R)-fluoro[ ²H₁]acetic acid ( 7a and 7b , resp.) in good yields. Their high isotopic and optical purity was established by ¹H- and ¹⁹F-NMR, mass, and circular-dichroism spectroscopy.     

Determination of drug-cyclodextrin binding constants by capillary zone electrophoresis

Binding constants of the optical isomers of Deprenyl® (selegiline) and its potential metabolites with (2,6-di-O-methyl)--cyclodextrin were determined using electrophoretic mobility data gained from separations performed by capillary electrophoresis, and absorbancies obtained from spectrophotometric experiments. To calculate equilibrium constants l: l complex formation have been assumed. The comparison of the equilibrium constants calculated from different methods shows similar values in their order of magnitude. Their difference may probably be explained by the different media of the measurements. The effect of the structure of compounds on chiral discrimination were also elucidated.