Angewandte Chemie International Edition in English

Cover image for Vol. 17 Issue 4

April 1978

Volume 17, Issue 4

Pages 221–291

Currently known as: Angewandte Chemie International Edition

  1. Reviews

    1. Top of page
    2. Reviews
    3. Communications
    4. Abstracts
    5. Book Reviews
    1. Quantitative Mass Spectrometry in Biochemistry and Medicine (pages 221–238)

      Dr. W. D. Lehmann and Dr. H.-R. Schulten

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.197802213

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      The principal applications of mass-spectrometric detection methods combined with gas-chromatographic resolution (GC-MS) include studies on the pharmacokinetics of drugs and active metabolites and confirmation of medical diagnoses. Using standards labeled with stable isotopes it is possible to conduct quantitative analyses in the picogram range.

    2. Photoacoustic Spectroscopy of Condensed Matter (pages 238–245)

      Dr. R. B. Somoano

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.197802381

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      A new nondestructive analytical procedure, photoacoustic spectroscopy, provides information about the electronic excitation spectra of substances (powders, gels, biological tissue, etc.) which are difficult to investigate by conventional techniques. The method, which complements fluorescence spectroscopy, can also be applied to samples that scatter the incident light.

    3. 17O-NMR Spectroscopy as a Structural Probe (pages 246–254)

      Prof. Dr. Walter G. Klemperer

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.197802461

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      Structural studies on oxygen compounds (e.g.β-Mo8Omath image) can utilize 17O-NMR spectroscopy, for non-equivalent oxygen atoms exhibit large differences in their chemical shifts. The availability of 17O-enriched material and FT-NMR instrumentation should lead to extensive use of this technique.

    4. Sodium-23 Nuclear Magnetic Resonance Spectroscopy (pages 254–266)

      Prof. Dr. Pierre Laszlo

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.197802541

      A spectroscopic technique that can be used for direct studies on phenomena of solvation and ion pair formation is 23 Na-NMR spectroscopy. Development of FT instruments has transformed this method into a valuable analytical tool. Naturally occurring sodium contains 100% of 23Na; no enrichment is therefore necessary.

  2. Communications

    1. Top of page
    2. Reviews
    3. Communications
    4. Abstracts
    5. Book Reviews
    1. A New Method for Selective Activation of Amino, Hydroxy, and Mercapto Carboxylic Acids at the Carboxyl Group: Preparation of Thiol and Selenol Esters (pages 267–268)

      Dr. Hans-Joachim Gais and Thomas Lied

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.197802671

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      Effective new acylating agents, the enol esters (3), are accessible by selective reaction of the ketone (1) with carboxylic acids (2) containing OH, NH2, or SH groups. The stable enol esters (3) (yields >90%) are transformed into thiol esters (4), X[DOUBLE BOND]S, in good yields on reaction with alkali metal thiolates. Potential applications exist in the synthesis of macrolides and peptides.

    2. A New Helical Molecular Skeleton (pages 268–269)

      Prof. Dr. Fritz Vögtle and Erich Hammerschmidt

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.197802681

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      A helical sequence of non-annelated aromatic rings is present in compound (1), which has now been synthesized. Plus ⇌ minus transitions of (1) and some analogous compounds with other bridges can be examined by NMR spectroscopy.

    3. Consecutive Nucleophilic and Electrophilic Attack on N2 Ligands: Synthesis of Azo Compounds from Molecular Nitrogen (pages 269–270)

      Prof. Dr. Dieter Sellmann and Dr. Woldemar Weiss

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.197802691

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      The reduction of coordinated dinitrogen has now been achieved by nucleophilic addition of methyl anions. The reduction product was trapped by methyl cations. Thus the catalytic synthesis of azomethane from N2 is possible in principle.

    4. An Unusual Benzene/Benzene Through-Space Interaction (pages 271–272)

      Prof. Dr. Horst Prinzbach, Dipl.-Chem. Gottfried Sedelmeier, Dr. Carl Krüger, Dr. Richard Goddard, Prof. Dr. Hans-Dieter Martin and Prof. Dr. Rolf Gleiter

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.197802711

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      Through-space interaction, comparable with that found in cyclophanes, occurs in compound (2), obtained from (1) in a multistep reaction. The molecule reduces benzene/benzene compression by angle widening; the planes of the benzene rings are mutually inclined by 18.6°

    5. Aluminum Tris(dihydrogen Phosphate) (pages 272–273)

      Dr. Rüdiger Kniep and Dipl.-Chem. Michael Steffen

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.197802721

      The crystal structure of AI(H2PO4)3 is characterized by an almost centrosymmetric arrangement of the heavy atoms which is rendered significantly acentric merely by the orientation of the protons. Since a polar axis is also present, ferroelectricity should be possible.

    6. An Arsinidene as a Cubane-Type Structural Unit: Synthesis and Structure of [(CO)3Fe—AsCH3]4 (pages 273–274)

      Dipl.-Chem. Erika Röttinger and Prof. Dr. Heinrich Vahrenkamp

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.197802731

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      The first cubane complex of iron to contain no sulfur has the formula [(CO)3Fe[BOND]AsCH3]4 Its synthesis utilized the thermolability of the As[BOND]H bond in complexes: (CO)4Fe.CH3AsH2 decomposes slowly at room temperature, and faster on heating, to form the Fe4As4 Cubane.

    7. 2,4,6-Tri-tert-butylphenoxyl (TBPO) as Sterically Active Carbonyl-Protecting Group—A New Nucleophilic Dimethylaminomethylating Reagent (page 274)

      Prof. Dr. Dieter Seebach and Dipl.-Chem. Tillmann Hassel

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.197802741

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      The (CH3)2 NCHmath image synthon is now readily accessible, thanks to a new sterically effective carbonyl-protecting group. The parent N, N-dimethylcarbamate reacts with sec-butyllithium to give (1), in which lithium can be replaced by electrophiles. Reduction with LiAlH4 leads via removal of the protecting group to products of type (CH3)2NCH2E.

    8. Reactivity of a Solfonium Ion in Layer Silicates of Montomorillonite Type (pages 274–275)

      Prof. Dr. Jürgen Gosselck and Dr. Ingfried Stahl

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.197802742

      Free R3 S+ ions and those intercalated in layer silicates react very differently. While the free S-benzyltetrahydrothiophenium ion fails to react with arenes, on intercalation in bentonite the ion reacts with benzene, toluene, anisole, chloro-benzene, etc. to give (o-and p-subtituted) aryl(phenyl)methanes. The reaction takes place in the interlamellar space; yields are good.

    9. Hexafluorophosphate of the Bis(naphthalene) Radical Cation (pages 275–276)

      Prof. Dr. Heniz P. Fritz, Dr. Helmut Gebauer, Dipl.-Chem. Peter Friedrich and Dr. Ulrich Schubert

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.197802751

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      Precise stacking of naphthalene units is found in the salt (C10H8)2PF6 which is generated electrochemically and contains the bis(naph-thalene) radical cation. The spacing between the C10H8 units (320pm) is the lowest yet found between arene rings and suggests pronounced interaction between the π-systems.

    10. Tris[(N,N,N′,N′-tetramethylethylenediamine)-lithium]hexamethylerbate(III) and -lutetate(III) (page 276)

      Prof. Dr. Herbert Schumann and Dipl.-Chem. Jochen Müller

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.197802761

      The first peralkylated complexes of metals in the lanthanoid series have now been synthesized. The compounds are extremely sensitive to air and moisture but decompose only slowly at their melting points of 138–139°C (M [DOUBLE BOND] Er) and 141–142°C (M [DOUBLE BOND] Lu).

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    11. C4Li4, Tetralithiotetrahedrane? (pages 276–278)

      Dipl.-Chem. Gerhard Rauscher, Dr. Timothy Clark, Dr. Dieter Poppinger and Prof. Dr. Paul von Ragué Schleyer

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.197802762

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      A monomeric substance of empirical formula C4Li4 has been obtained by irradiation of dilithioacetylene in liquid NH3 at −45°C. 13C-NMR spectrum and field-desorption mass spectrum are compatible with the idea that C4Li4 is a derivative of the long-sought species tetrahedrane. Ab initio MO calculations show the face-centered structure (1) to be more favorable than other structures of high symmetry.

    12. Deprotonation-Hydride Elimination as a Method of Dehydrogenation (pages 278–279)

      Doz. Dr. Manfred T. Reetz and Dipl.-Chem. Franz Eibach

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.197802781

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      The aromatization of dihydroarenes, which in some cases (e.g. synthesis of 9,10-dialkylanthracenes) was formerly only possible by devious means, can now be accomplished with potassium fencholate (1) as base and fenchone (2) as hydride acceptor. Since (1) is regenerated, only catalytic amounts are required.

    13. [(S2)2Mo(S2)2Mo(S2)2]2−, a Novel Complex Containing Only Smath image Ligands and a Mo[BOND]Mo Bond (page 279)

      Prof. Dr. Achim Müller, Dipl.-Chem. Wulf-Otto Nolte and Prof. Dr. Bernt Krebs

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.197802791

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      Mo-S compounds occur in redox enzymes whose action involves electron transfer MoVI⇌MoV. In this context, interest attaches to the new complex (1), which is formed on reduction of molybdate(VI) by polysulfide ions in aqueous solution. In (1), Mo has the unusual coordination number 9.

    14. A One-Step Synthesis of Vinylsilanes and Vinylenebissilanes (pages 279–280)

      Hideyuki Matsumoto, Shigeru Nagashima, Takayuki Kato and Prof. Dr. Yoichiro Nagai

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.197802792

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      A convenient entry to vinylsilanes (silylethenes)(1) is provided by the homogeneously catalyzed reaction shown below. trans-1,2-Dichloroethene gives vinylenebissilanes. These organosilicon compounds and (1) are of interest as reagents in organic and polymer chemistry.

    15. Molecular Structure of [Mn(CO)4NSOF2]2— A Dinuclear Transition Metal Complex Containing Difluorooxosulfimidato Bridges (pages 280–281)

      Dr. Bruno Buss, Dr. Dieter Altena, Priv.-Doz. Dr. Rüdiger Mews and Prof. Dr. Oskar Glemser

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.197802801

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      The bonding in complex(1) can be described in two alternative ways. No decision is yet possible between (1a) (MnI, NSOF2 as four-electron donor) and (1b) (Mn0, NSOF2 as three-electron donor) on the basis of available experimental data, including X-ray structure analysis.

    16. N,N-Dichlorourethane—A Selective Chlorination Reagent; Synthesis of Corticoids (pages 281–282)

      Prof. Dr. Yehuda Mazur and Zvi Cohen

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.197802811

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      Introduction of a double bond between C-9 and C-11 of the steroid skeleton can be accomplished by (i) chlorination of the saturated steroid with N, N-dichlorourethane (EtO[BOND]CO[BOND]NCl2) followed by (ii) dehydrochlorination with AgClO4. The products, e.g.(1), can easily be functionalized at C-11.

    17. Organic Syntheses Using Sheet Silicate Intercalates: Low-temperature Conversion of Olefins to Secondary Ethers (pages 282–283)

      Dr. John M. Adams, Dr. James A. Ballantine, Dr. Samuel H. Graham, Dr. Richard J. Laub, Prof. J. Howard Purnell, Paul I. Reid, Wafa Y. M. Shaman and Prof. John M. Thomas

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.197802821

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      Water intercalated in montmorillonites can react with 1-alkenes (1) to give secondary ethers (2). Efficient preparations of (2) were hitherto unknown. The cations of the layer silicate must be exchanged, preferably for Cu2+, prior to the reaction.

    18. Alkali Metal Salts of RC(O)-Substituted Cyclononatetraenyl Anions: Aromatic [9] Annulene Anion or Olefinic Nonafulvene Structure as Function of Gegenion and Solvent (pages 283–284)

      Priv.-Doz. Dr. Gernot Boche and Dipl.-Chem. Frank Heidenhain

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.197802831

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      The aromaticity of an organic anion has now been found to depend upon ion-pair character; this discovery was made with the anion of 9-acetylcyclononatetraene (1). In THF, (2) contains an aromatic anion and (3) an olefinic anion.

    19. Reduction of 1,3-Diphenylallyl Anions via Dianion Radicals to Trianions with Lithium, Sodium, Potassium, and Cesium as Gegenions (pages 284–285)

      Priv.-Doz. Dr. Gernot Boche and Dipl.-Chem. Klaus Buckl

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.197802841

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      Alkali metal salts of di- and triphenylallyl trianions(1) have now been prepared for the first time by electron-transfer reactions. (1), R[DOUBLE BOND]R′[DOUBLE BOND]Ph, M[DOUBLE BOND]Cs, is stable in THF, even at room temperature. The structure of (1) is proved, inter alia, by reaction with electrophiles (H2O, D2O, Me2SO4, etc.) to give hydrocarbons (2).

    20. Demonstration of “Sulfene” Insertion into the Metal-Hydrogen Bond (pages 285–286)

      Dr. Ingo-Peter Lorenz

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.197802851

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      Insertion of H2C[DOUBLE BOND]SO2 (“sulfene”) into the M[BOND]H bond has been established by experiments with CpW(CO)3D. The mild conditions of this reaction should permit the synthesis of numerous sulfinato-S complexes, including thermally unstable species.

    21. Structural Changes during the Oxidation of B-, C-, Si-, and P-Substituted Hydrazines (pages 286–288)

      Prof. Dr. Hans Bock, Dr. Wolfgang Kaim, Dr. Andrzej Semkow and Prof. Dr. Heinrich Nöth

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.197802861

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      The transformation of substituted hydrazines into (stable) radical cations has been studied by PE and ESR spectroscopy. The gas-phase ionizations recorded by PE spectroscopy occur so fast that the molecular structure cannot change; in contrast, oxidation in solution leads to radical cations (studied by ESR spectroscopy) having energetically preferred structures (stabilized by flattening).

  3. Abstracts

    1. Top of page
    2. Reviews
    3. Communications
    4. Abstracts
    5. Book Reviews
    1. ABSTRACTS (pages 288–289)

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.197802881

  4. Book Reviews

    1. Top of page
    2. Reviews
    3. Communications
    4. Abstracts
    5. Book Reviews
    1. Book Review: Modern Practice of Chromatography. By R. L. Grob (page 291)

      Wilfried A. König

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.197802911

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