Angewandte Chemie International Edition in English

Cover image for Vol. 18 Issue 2

February 1979

Volume 18, Issue 2

Pages 91–172

Currently known as: Angewandte Chemie International Edition

    1. Cover Picture (Angew. Chem. Int. Ed. Engl. 2/1979)

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.197900911

    2. Graphical Abstract (Angew. Chem. Int. Ed. Engl. 2/1979)

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.197900912

  1. Reviews

    1. Top of page
    2. Reviews
    3. Communications
    4. Book Reviews
    1. Structure and Bonding in Cyclic Sulfur-Nitrogen Compounds (pages 91–97)

      Prof. Dr. Herbert W. Roesky

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.197900913

      Thumbnail image of graphical abstract

      The scope and variety of sulfur-nitrolgen rings become more comprehensible on adopting the coordination number of sulfur as a classification principle. In compounds of two-coordinate sulfur (and nitrogen) the π-electrons are largely delocalized; the coordination number and bond length can be correlated in some compounds of sulfur with higher coordination number.

    2. Empirical Parameters of Solvent Polarity as Linear Free-Energy Relationships (pages 98–110)

      Prof. Dr. Christian Reichardt

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.197900981

      Effects of solvents on the rates of chemical reactions and on equilibria have long been known, but there are still no reliable methods for their description and prediction. Empirical parameters derived, e.g. from series of reactions, are of great value in this connection.

    3. New Applications of Computers in Chemistry (pages 111–123)

      Prof. Dr. Ivar Ugi, Dipl.-Inform Johannes Bauer, Dr. Josef Brandt, Dipl.-Inform. Josef Friedrich, Dr. Johann Gasteiger, Dr. Clemens Jochum and Dr. Wolfgang Schubert

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.197901111

      Thumbnail image of graphical abstract

      The design of entirely new syntheses, and the classification and documentation of structures, substructures, and reactons are examples of new applications of computers to chemistry. The starting point is a mathematical model of constitutional chemistry based on the extension of the concept of isomerism to ensembles of molecules.

    4. Activation Analysis—Its Present State of Development and Its Importance as an Analytical Tool (pages 123–147)

      Prof. Dr. Viliam Krivan

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.197901231

      Thumbnail image of graphical abstract

      The feasibility of simultaneous multielement determinations is one of the particular advantages of activation analysis. This trace analytical method can detect many elements and isotopes at concentrations below the ppb level.

  2. Communications

    1. Top of page
    2. Reviews
    3. Communications
    4. Book Reviews
    1. Synthesis of the Mast Cell Degranulating (MCD) Peptide from Bee Venom (pages 147–148)

      Priv.-Doz. Dr. Christian Birr and Dr. Margot Wengert-Müller

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.197901471

      Potential value in the therapy of rheumatism and other inflammation processes could attach to the MCD peptide from bee venom if it were available in larger quantities. The peptide consists of 22 amino acids and contains two disulfide bridges. Its first total synthesis has now been accomplished.

    2. Selective Electrochemical Removal of Protecting Groups in Nucleotide Synthesis (pages 148–149)

      Dr. Joachim Engels

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.197901481

      Thumbnail image of graphical abstract

      Selective removal of an ester group from the completely protected nucleoside 3′-phosphate(2) by electrochemical reduction solves a serious problem of nucleotide synthesis. Reaction (2) [RIGHTWARDS ARROW] (3) requires a potential of −0.5 V; (2) [RIGHTWARDS ARROW] (1) can be accomplished by acid hydrolysis. At −1.2 V the remaining ester groups are removed from (1).

    3. Di-tert-Butyl Acetylenedicarboxylate and Its Cyclotrimerization (pages 149–150)

      Prof. Dr. Wolfgang Sucrow and Dr. Fritz Lübbe

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.197901491

      Di-tert—butylacetylenedicarboxylate(1)—surprisingly not synthesized before—is remarkable from a chemical standpoint. Its cyclotrimerization shows that the tert-butyl groups do not exert strong steric hindrance. Ready cleavage (without base) of the esters obtained from (1) is of advantage.

      • equation image
    4. Synthesis and Properties of Tetrabutylammonium Octaiododirhenate(III),[(n-C4H9)4N]2[Re2I8] (pages 150–151)

      Prof. Dr. Wilhelm Preetz and Dipl.-Chem. Lutz Rudzik

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.197901501

      Salts of the anion [Re2I8]2−, containing a ReRe quadruple bond, have hitherto defied preparation. However, they are accessible by reaction in nonaqueous solution. The HI used should be free from water and iodine (X[DOUBLE BOND]CL, Br).

      • equation image
    5. Long-Chain Alkylammonium Ions as Phase Transfer Reagents for the Synthesis of Mixed-Ligand Complexes of the Platinum Metals (pages 151–152)

      Dipl.-Chem. Ashok Kumar Shukla and Prof. Dr. Wilhelm Preetz

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.197901511

      Phase transfer reactions have great preparative potential in inorganic chemistry. Thus the first halo complexes of Os, Ir, Pt, and Re have now been synthesized in the presence of [(C12H25)3NH]HSO4; they contain not only fluorine but also bromine and iodine as ligands. The following anions are examples (X[DOUBLE BOND]CL or Br):

      • equation image
    6. Detection of Large-Ring Sulfur Molecules in Liquid Sulfur: Simple Preparation of S12, α-S18, and S20 from S8 (pages 152–153)

      Prof. Dr. Ralf Steudel and Dipl.-Chem. Hans-Joachim Mäusle

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.197901521

      The molecular composition of liquid sulfur has been a topic of discussion for generations. It was known to contain the homocyclic species S6 and S7, as well as S8. The isolation of S12, α-S18, and S20, and the detection of Sx with x = 23—34 are new accomplishments.

    7. 23Na-NMR Study of the Competition of Biogenic Amines with Sodium Ion for Binding to Lasalocid (X-537A) (pages 153–154)

      Dr. Jean Grandjean and Prof. Dr. Pierre Laszlo

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.197901531

      Thumbnail image of graphical abstract

      Lasalocid (X-537 A) (1), an ionophoric antibiotic, complexes both biogenic amines and inorganic cations. It has now been established that Na+ and serotonin bimaleate, 3-hydroxytyramine, or L-norepinephrine compete for binding to (1).

    8. Reversal of the Selectivity Principle in Free-Radical Addition to Alkenes (pages 154–155)

      Prof. Dr. Bernd Giese and Dipl.-Chem. Jürgen Meixner

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.197901541

      The selectivity of alkenes in radical reactions increases with increasing reactivity, i.e. the most selective alkenes are the most reactive ones. This result could be of interest, say in radical polymerization.

    9. A New Cationic Binuclear Trihydrido Complex Containing One Four-and One Five-Coordinate Platinum Atom (pages 155–156)

      Gustav Bracher, Dr. David M. Grove, Dr. Paul S. Pregosin and Prof. Luigi M. Venanzi

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.197901551

      Thumbnail image of graphical abstract

      Two Pt and three H atoms, together with four PPh3 groups, make up the cation of complex (1), R[DOUBLE BOND]Ph, which can be isolated as yellow, air-stable crystals. The remarkable structure was elucidated by NMR spectroscopy.

    10. Stable Aza- and Diazacyclopentadienylium Salts (pages 156–157)

      Prof. Dr. Rudolf Gompper and Dipl.-Chem. Klaus Bichlmayer

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.197901561

      Thumbnail image of graphical abstract

      Aza-analogues of the antiaromatic cyclopentadienyl cations are present in the salts (1) and (2). The antiaromatic character of the azacations is weaker than that of the parent cation; the donor groups contribute to stabilization.

    11. An Example of the Equilibrium Ethylenehydridometal ⇌ Ethylmetal Complex (pages 157–158)

      Prof. Dr. Helmut Werner and Dipl.-Chem. Rainer Feser

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.197901571

      An understanding of the processes involved in the insertion of olefins into M[BOND]H bonds is important for many catalytic processes. Equilibrium between an ethylenehydrido-metal (1) and an ethyl-metal complex (2) in solution has been demonstrated for the first time.

      • equation image
    12. Stepwise Addition of a Lewis Acid and a Lewis Base to a Metal-Metal Bond (pages 158–159)

      Prof. Dr. Helmut Werner and Dipl.-Chem. Werner Hofmann

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.197901581

      Thumbnail image of graphical abstract

      Cleavage of the Co[DOUBLE BOND]Co bond in the complex is feasible without disrupting the binuclear structure. Thus a Lewis acid, e.g. CF3COOH, and a Lewis base. e.g. PMe3, can be added successively to (1).

    13. Hindered Rotation at the Triple Bond (pages 159–161)

      Philippe Koo Tze Mew and Fritz Vögtle

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.197901591

      Thumbnail image of graphical abstract

      Rotation within the linear

      group can be hindered by substituents; the first example is bis(dimethyltriptycenyl)ethyne (1), Ri[DOUBLE BOND]Ra[DOUBLE BOND]CH3. Stuart-Briegleb space-filling models do not reproduce this effect.

    14. Surprising Transformation of Azulene by Cycloaddition with 1-(Diethylamino)propyne (pages 161–162)

      Prof. Dr. Klaus Hafner, Prof. Dr. Hans Jörg Lindner and Dipl.-Ing. Werner Ude

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.197901611

      Thumbnail image of graphical abstract

      The cyclopentacyclononene derivative(3). the first compound to contain this ring system and also the first stable cyclononatetraene not to have an annelated benzene ring, has been synthesized from the “ethanoazulene” (1). This synthesis is possible because azulene reacts readily with the ynamine (2), to give the tricyclic species (4). Although 4,6,8-methylazulene initially gives the desired ring system (5), immediate transannular bonding occurs. The bracket in (1) prevents this reaction.

    15. Facile Ring Enlargement of Azulene to Give the Cyclopentacyclononene System by Dipolar Cycloaddition (pages 162–163)

      Prof. Dr. Klaus Hafner, Prof. Dr. Hans Jörg Lindner and Dipl-Ing. Werner Ude

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.197901621

      Thumbnail image of graphical abstract

      The cyclopentacyclononene derivative(3). the first compound to contain this ring system and also the first stable cyclononatetraene not to have an annelated benzene ring, has been synthesized from the “ethanoazulene” (1). This synthesis is possible because azulene reacts readily with the ynamine (2), to give the tricyclic species (4). Although 4,6,8-methylazulene initially gives the desired ring system (5), immediate transannular bonding occurs. The bracket in (1) prevents this reaction.

    16. 3-Bromo-3-methyl-2-trimethylsiloxy-1-butene—A New Cycloaddition Reagent (pages 163–164)

      Prof. Dr. Hideki Sakurai, Dipl. Chem. Akihiko Shirahata and Dr. Akira Hosomi

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.197901631

      Thumbnail image of graphical abstract

      A facile entry to cycloheptenones and cyclopentanones is provided by the new cyclization reagent (1). Examples are the synthesis of Karahanaenone (2) from isoprene, and of(±)-α-cuparenone (4), R = p-CH3[BOND]C6H4, from 1-isopropenyl-4-methylbenzene.

    17. Faclie Regeneration of Carbonyl Compounds from 1,3-Dithiane 1-Oxides via 1-Ethoxy-1,3-dithianium Salts (pages 165–166)

      Dr. Ingfried Stahl, Jürgen Apel, Dipl.-Chem. Rainer Manske and Prof. Dr. Jürgen Gosselck

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.197901651

      Thumbnail image of graphical abstract

      Liberation of aldehydes R[BOND]CH[DOUBLE BOND]O from dithiane oxides(1) can be accomplished by transformation into the salts (3) and their cleavage with water. The reaction sequence (1)[RIGHTWARDS ARROW](3) [RIGHTWARDS ARROW] R[BOND]CH[DOUBLE BOND]O is milder than the usual cleavage of (1) with acid.

    18. Bond Switch with Participation of π-Bonded SIV in Thiathiophthene-Analogous Systems (pages 166–167)

      Prof. Dr. Kin-ya Akiba, Dipl. Chem. Shin-ichi Arai, Dr. Tohru Tsuchiya, Yohsuke Yamamoto and Prof. Dr. Fujiko Iwasaki

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.197901661

      Thumbnail image of graphical abstract

      Dynamic bond switching at π-hypervalent sulfur has now been demonstrated. (1) and (2) rapidly equilibrate; this reaction involves the thiathiophtheneanalogous system (3).

    19. Synchronous Mechanism of the 1,1-Cycloaddition of Nitrile Ylides to C[DOUBLE BOND]C Double Bonds (pages 167–168)

      Dr. Janos Fischer and Prof. Dr. Wolfgang Steglich

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.197901671

      Thumbnail image of graphical abstract

      An insight into the mode of reaction of nitrile ylides such as (1) has come from the study of their intramolecular cyloaddition to double bonds. The formation of (2a) and (2b) in the ratio 9:1 is assessed as indicating a synchronous mechanism (R[DOUBLE BOND]p[BOND]CL—C6H4).

    20. Smath image as Simultaneous End-on and Side-on Bonded Ligand in the Novel Transition-Metal Complex [Mo4(NO)4S13]4− (pages 168–169)

      Prof. Dr. Achim Müller, Dipl.-Chem. Werner Eltzner and Dr. Nageswaran Mohan

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.197901681

      Thumbnail image of graphical abstract

      Five different bonding states of sulfur are found in complex (1). It is a further example of the importance of Smath image ligands in the stabilization of unusual coordination compounds of transition metals.

    21. Bis(chlorophenylphosphoranediyl)methane (page 169)

      Prof. Dr. Rolf Appel and Dipl.-Chem. Karl Waid

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.197901691

      Thumbnail image of graphical abstract

      A new synthetic unit for phosphorus-carbon compounds has been discovered in the symmetrical “carbodiphosphorane” (2). It forms a 1:1 salt with HCL, and a dioxide (via elimination of RCL) with alcohols ROH.

    22. Flash Vacuum Thermolysis of Doubly Unsaturated Acyl Halides to Give Phenols (page 170)

      Prof. Dr. Eckehard V. Dehmlow and Marion Slopianka

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.197901701

      Thumbnail image of graphical abstract

      The simplest dienylketene-phenol rearrangement has been achieved by vacuum flash thermolysis of sorboyl chloride at 6 × 10−5 torr/660°C. Other dienylketenes can also be generated under these conditions.

  3. Book Reviews

    1. Top of page
    2. Reviews
    3. Communications
    4. Book Reviews
    1. Book Review: Collision Spectroscopy. Ed. by R. G. Cooks (pages 171–172)

      Helmut Schwarz

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.197901713

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