Angewandte Chemie International Edition in English

Cover image for Vol. 18 Issue 4

April 1979

Volume 18, Issue 4

Pages 239–336

Currently known as: Angewandte Chemie International Edition

  1. Reviews

    1. Top of page
    2. Reviews
    3. Communications
    4. Book Reviews
    1. Methods of Reactivity Umpolung (pages 239–258)

      Prof. Dr. Dieter Seebach

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.197902393

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      Planning of the synthesis' of an organic target molecule is greatly facilitated by distinguishing between reagents with normal reactivity and those with reactivity umpolung. This systematic survey of methods available for achieving umpolung shows normal reactivity in green print while reactivity umpolung is indicated by red print.

    2. Alkenediazonium Salts: A New Chapter of Classical Organic Chemistry (pages 259–265)

      Dr. Kaspar Bott

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.197902591

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      Alkenediazonium salts(1) were considered non-isolable just a few years ago. Meanwhile, many salts of this kind have been synthesized and isolated; a general synthetic route is shown below (LA = Lewis acid).

    3. Kinetics of Sorption, Desorption, and Diffusion in Zeolites (pages 266–272)

      Dr. Hans-Joachim Doelle and Prof. Dr. Lothar Riekert

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.197902661

      Three coupled process are involved in sorption and desorption in zeolites (molecular sieves): diffusion in the crystals, mass transfer in the intracrystalline voids, and heat transfer between the sorbent surroundings.

    4. Polymer Alloys—Their Structure, Morphology, and Properties (pages 273–295)

      Dr. Burghard J. Schmitt

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.197902731

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      Demands for new properties of polymeric materials are being increasingly met by combination (“alloying”) of known polymers. Thus, incorporation of a polybutadiene latex in a polystyrene matrix gives glass-clear two-phase systems.

    5. Chemical Vapor Deposition of Silicon Carbide and Silicon Nitride—Chemistry's Contribution to Modern Silicon Ceramics (pages 295–304)

      Prof. Dr. Erich Fitzer and Dr. Dieter Hegen

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.197902951

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      Pure SiC and Si3N4 in bulk pore-free form have valuable properties; however, their industrial exploition has hardly been possible up to now. Chemical vapor deposition provides a means of filling the pores in both these materials.

  2. Communications

    1. Top of page
    2. Reviews
    3. Communications
    4. Book Reviews
    1. A New Entry to Naphthalene Oxides (pages 304–305)

      Prof. Dr. Richard R. Schmidt and Dipl.-Chem. Rolf Angerbauer

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.197903041

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      A facile synthesis of epoxy diols and diepoxides from arenes proceeds via arynes and should therefore be relatively versatile. The products are of interest as carcinogenic metabolities of aromatic hydrocarbons.

    2. ω-Formyl-and 4-Oxocarboxylic Acids in Blood Plasma (pages 305–306)

      Dipl.-Chem. Jürgen Pfordt and Prof. Dr. Gerhard Spiteller

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.197903051

      GC/MS studies on blood plasma have shown that formyl- and oxo-carboxylic acids also occur in the dicarboxylic acid fraction. Molecular ions do not appear in the mass spectrum; the molecular weights were determined from the M[BOND]OCH3 fragments of the esters.

    3. Diastereoselective Synthesis of β-Methyl Homoallyl Alcohols (pages 306–307)

      Prof. Dr. Reinhard W. Hoffmann and Dipl.-Chem. Hans-Joachim Zeiss

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.197903061

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      Macrolide antibiotics and other natural products and active compounds contain β-methylalkanol structural units which can now be synthesized diastereoselectively with the aid of the adaptable synthetic unit (1).

    4. Economic Synthesis of Activated N-tert-Butyloxycarbonyl Amino Acid Esters (pages 307–308)

      Dipl.-Chem. Gerd Schnorrenberg and Prof. Dr. Wolfgang Steglich

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.197903071

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      Activated Boc-amino acid esters(2)—suitable e.g. for peptide syntheses—can be produced particularly economically by twofold use of reagant (1).

    5. Electrophilic Behavior of Tri-tert-butylcyclobutadiene (page 308)

      Prof. Dr. Günther Maier and Fritz Köhler

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.197903081

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      The chemical “omnipotence” of the cyclobutadiene derivates(1) is substantaited by the discovery of its surprising electrophilic properties. This result can be regarded as chemical proof of a Jahn-Teller effect.

    6. Ester and Lactone Formation with the Reagent 1,2-Dihydro-4,6-dimethyl-2-thioxo-3-pyridinecarbonitrile (pages 308–309)

      Prof. Dr. Ulrich Schmidt and Dr. Dieter Heermann

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.197903082

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      Transformation of long-chain ω-hydroxy acids into the macrolactone can be accomplished with the title compound. The disulfied derived therefrom is esterified with the acid to give (1); on heating (1) gives the lactone. The thiol esters (1) are less expensive and more readily accessible than comparably reactive lactone precursors.

    7. Directed Synthesis of Acyl Ortho Esters (pages 309–310)

      Prof. Dr. Günter Wulff, Dipl.-Chem. Ulrich Schröder and Dr. Wolfram Schmidt

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.197903091

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      Acyl ortho esters such as (1)—postulated as intermediates in neighboring group reactions—have now been produced by a directed synthesis. These highly reactive compound could be of use in the production of 1,2-trans-glycosides.

    8. Lactide Contraction—A Method for the Synthesis of α,α′-Dihydroxy Ketones from α-Hydroxy Carboxylic Acids (pages 310–311)

      Prof. Dr. Ulrich Schöllkopf, Dr. Wolfgang Hartwig, Dipl.-Chem. Uwe Sprotte and Dr. Werner Jung

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.197903101

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      Hydroxy ketones and dihydroxy ketones(4), R4 = alkyl, H, are versatile synthons. Key step in their formation from α-hydroxy carboxylic acids and β-bromo acyl cholorides via (1) is the contraction (2) [RIGHTWARDS ARROW] (3).

    9. Crown Ethers with Fluctuating Ring Size (“Breathing Crown Ethers”) (pages 311–312)

      Prof. Dr. Gerhard Schröder and Dipl.-Chem. Walter Witt

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.197903111

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      Novel compounds of variable ring size have been obtained by combining structural components of bullvalence and crown ethers. The macrocyclic part can become reversibly larger or smaller depending upon the supply of thermal enenrgy.

    10. Aza [18]annulenes (pages 312–313)

      Dipl.-Chem. Walter Gilb and Prof. Dr. Gerhard Schröder

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.197903121

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      The first monocyclic vinylog of pyridine with (4n+2)π electrons—i.e. an “aromatic” aza[18]annulene—has been obtained by a multistep synthesis as greennish black crystals. The nitrogen occupies an internal position.

    11. The Double Salt Na2S2O5 · NaOOCH as Intermediate in the Formation of Sodium Dithionite by Reduction of SO2 with Sodium Formate (pages 313–314)

      Dr. Gert Ertl, Dr. Volker Kiener, Dr. Werner Ostertag and Dr. Gerd Wunsch

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.197903131

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      The formation of sodium dithionite (Na2S2O4) from SO2 and sodium formate in a three-phase system proceeds via the double salt Na2S2O5·NaOOCH which has now been isolated in crystalline form (see photograph). Na2S2O4 is of importance in vat dyeing and in bleaching.

    12. α,β-Unsaturated Isocyanates by Thermolysis of N-(1-Alkenyl)-N-alkylcarbamoyl Chlorides (pages 319–320)

      Dr. Karl-Heinz König, Dr. Christan Reitel, Dr. Dietrich Mangold, Dr. Karl-Heinz Feuerherd and Dr. Heinz-Günter Oeser

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.197903191

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      Vinyl isocyanates are now accessible on a kilogram scale by a safe new route. Thermolysis of (1) is the key step.

    13. Iminocarbene/Ketenimine Rearrangement (page 320)

      Dipl.-Chem. Bernhard Arnold and Prof. Dr. Manfred Regitz

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.197903201

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      α-Iminocarbenes(1)—now readily accessible by a new route—have been observed to undergo novel rearrangement to the hitherto unknown aminoketenimines (2). The latter compounds react with methanol to give (3). A certain proportion of (1) undergoes “normal” stabilization via addition of methanol (R[DOUBLE BOND]C6H5).

    14. Selective Deuteration of Enamines with Deuterated Formic Acids (pages 320–321)

      Dr. Walter Himmele, Dr. Wolfgang Bremser and Dr. Hardo Siegel

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.197903202

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      Selective isotopic lebeling is very important for elucidating the metabolites of active substances. It can be accomplished by reducing an enamine (R[DOUBLE BOND]4-tert-butylbenzy) with HCOOD, DCOOD, or DCOOH, e.g.

    15. Effects of Long-Chain Branches on the Degradation Kinetics of Polymers (pages 321–322)

      Prof. Dr. Klaus H. Ebert, Dr. Hanns J. Ederer and Dr. Arno Max Basedow

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.197903211

      Degradation of polymers in solution is greatly influenced by long side chains. Quantitative information about the number of branches and the length of the side chains etc., can be obtained from the molecular weight distribution by mathematical simulation.

    16. trans-Bis(1-alkynyl)-4B-metal Phthalocyanines (pages 322–323)

      Prof. Dr. Michael Hanack, Dipl.-Chem. Konrad Mitulla, Dipl.-Chem. Georg Pawlowskim and Dr. L. R. Subramanian

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.197903221

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      Model substances for new polymeric structures, predicted by EHMO calculations to have pronounced electrical conductivity, are seen in the new polymeric phthalocyanine derivatives of type (1) with R = 1-alkynyl (e.g. C[TRIPLE BOND]CPh, C[TRIPLE BOND]CMe), and M [DOUBLE BOND] Si, Ge, Sn.

    17. Characterization of Short-Lived Photoproducts by Pulse Raman Spectroscopy (pages 323–324)

      Dipl.-Chem. Walter Hub, Univ.-Doz. Dr. Siegfried Schneider and Prof. Dr. Friedrich Dörr

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.197903231

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      Photolysis of (1) in KBr and CCl4 leads to various products, as shown by the highly time-resolved Raman spectrum of transient photoproducts obtained for the first time. Accordingly, the radical (2) is formed in KBr and possibly the cation (3) in CCl4.

    18. Homogeneously Catalyzed Dimerization of Isoprene to 2,7-Dimethyl-2, trans-4,6-octatriene at Chromium (pages 324–325)

      Prof. Dr. Heindirk tom Dieck and Dipl.-Chem. Alois Kinzel

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.197903241

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      The tail-to-tail dimerization of isoprene to give (1) is accomplished in 80% yield on a 1,4-diaza-1,3-diene-modified chromium(0) catalyst. The absence of other isoprene suggests strong steric interaction during the first CC linkage.

    19. Novel Titanium Halides Containing Metal-Metal Bonds: Ti7Cl16 and Ti7Br16 (pages 325–326)

      Prof. Dr. Harald Schäfer, Dipl.-Chem. Reinhard Laumanns, Prof. Dr. Bernt Krebs and Dr. Gerald Henkel

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.197903251

      The discovery of two new titanium halides came as a surprise. The isotypic compounds Ti7Cl16 and Ti7Br16 are produced by chemical transport (via gaseous complexes); X-ray analysis shows them to contain Ti[BOND]Ti bonds.

    20. Bis(dichloroboryl)silylamines and Tris(dichloroboryl)-amine (pages 326–327)

      Dipl.-Chem. Theo Gasparis, Prof. Dr. Heinrich Nöth and Dr. Wolfgang Storch

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.197903261

      The first B-perhalogenated di- and triborylamines have been synthesized from RN(SnMe3)2 and N(SnMe3)3. The weakest B[BOND]N bonds yet encountered are found in Cl3SiN(BCl2)2 and N(BCl2)3.

      • equation image
    21. Complex-Stabilized Hydroxy (p-tolyl)acetylene by Reaction of trans-Chlorotetracarbonyl(tolylcarbyne)tungsten with Acetylacetone (pages 327–328)

      Prof. Dr. Ernst Otto Fischer and Dipl.-Chem. Peter Friedrich

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.197903271

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      An “acetylene alcohol”, which is stabilized by coordination to a transition metal to atom, arises on photochemical reduction of the carbyne complex (1) with acetylacetone. Crystal structure analysis shows the acetylene C atoms to be symmetrically bonded to the W atom.

    22. Photochemical Behavior of N2-Complexes: Photoluminescence of trans-(N2)2W(diphos)2 and trans-(CO)2W(diphos)2 (pages 328–329)

      Albert Caruana and Priv.-Doz. Dr. Horst Kisch

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.197903281

      The first photoluminescing dinitrogen complextrans-(N2)2W(diphos)2(1) is also the first transition-metal(o) compound to show a structured emission spectrum. These finding are of considerable significance for the photochemical reduction of complexed N2.

    23. [2.2.2.2](1,2,3,4,)Cyclophane (page 329)

      Dipl.-Chem. Jürgen Kleinschroth and Prof. Dr. Henning Hopf

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.197903291

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      The first phane to have four adjacent ethano bridges has been synthesized from a paracyclophane derivative. This completes the series of isomeric [2.2.2.2.] cyclophanes.

    24. Cycloadditions of α-Diazo Carbonyl Compounds to Enamines (pages 330–331)

      Prof. Dr. Rolf Huisgen and Dr. Hans-Ulrich Reissig

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.197903301

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      Carbonyl-activated diazo compounds and enamines (acyclic or with a six-membered ring) undergo 1,3-dipolar cycloaddition. The invariant orientation of the reactants is remarkable: the initial products are 4-aminopyrazolines such as (1). In contrast, the (partly isolable) zwitterions (2) formed as primary products from enamines with a five-membered ring arise by azo coupling.

    25. Azo Coupling of α-Diazo Carbonyl Compounds with N-(1-Cyclopentenyl)amines (pages 331–332)

      Prof. Rolf Huisgen, Dipl.-Chem. Werner Bihlmaier and Dr. Hans-Ulrich Reissig

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.197903311

      Thumbnail image of graphical abstract

      Carbonyl-activated diazo compounds and enamines (acyclic or with a six-membered ring) undergo 1,3-dipolar cycloaddition. The invariant orientation of the reactants is remarkable: the initial products are 4-aminopyrazolines such as (1). In contrast, the (partly isolable) zwitterions (2) formed as primary products from enamines with a five-membered ring arise by azo coupling.

    26. Oxidative Addition to a Quadruple Bond. The Complete X-ray Structure of [Mo2Cl8H]3− (pages 332–333)

      Dr. Avi Bino and Prof. Dr. F. Albert Cotton

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.197903321

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      Oxidatve addition to an M[TRIPLE BOND]M bond has now been demonstrated for the molybdenum compound (1) by X-ray structure analysis of the anion (2). The species (2) contains a symmetrically bridging H atom with appreciable hydride character.

      • equation image
    27. N2-(Trichlorovinyl)amidinees—New 1,3-Biselectrophilic Reagents (pages 333–334)

      Lic. Chim. Didier Van Broeck, Dr. Zdenek Janousek, Dipl.-Ing. Robert Merényi and Prof. Dr. Heinz Günter Viehe

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.197903331

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      Valuable diffunctional regents for heterocyclization have been found in trichlorovinylamidines such as (1). They can be prepared from trichlorvinyl isocynate.

  3. Book Reviews

    1. Top of page
    2. Reviews
    3. Communications
    4. Book Reviews

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