Angewandte Chemie International Edition in English

Cover image for Vol. 20 Issue 2

February 1981

Volume 20, Issue 2

Pages 135–216

Currently known as: Angewandte Chemie International Edition

  1. Reviews

    1. Top of page
    2. Reviews
    3. Communications
    4. Book Reviews
    5. Corrigenda
    1. Toxication of Foreign Substances by Conjugation Reactions (pages 135–142)

      Priv.-Doz. Dr. Dieter Reichert

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.198101353

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      The long held opinion that compounds foreign to organisms are in general detoxified to substances endogenous to the body by “conjugation” reactions, is no longer valid from the results of recent investigations. On the contrary, many xenobiotics are transformed in organisms into highly toxic, mutagenic and carcinogenic products—i.e. toxication rather than detoxication.

    2. Protein Differentiation: Emergence of Novel Proteins during Evolution (pages 143–151)

      Prof. Dr. Georg E. Schulz

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.198101431

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      The almost limitless number of proteins can be traced back to approximately 200 polypeptide geometries; these form the set from which traceable protein differentiation started. This differentiation begins with a gene duplication. Comparison of the amino acid sequences of equivalent proteins in two species yields the evolutionary distance between them. From this, the point in time when the species branched can be estimated (“molecular palaeontology”).

    3. Alkylsulfamoyl Chlorides as Key Units in the Synthesis of Novel Biologically Active Compounds for Crop Protection (pages 151–164)

      Dr. Gerhard Hamprecht, Dr. Karl-Heinz König and Dr. Gerd Stubenrauch

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.198101511

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      New synthetic routes to the versatile bifunctional alkylsulfamoyl chlorides RNH[BOND]SO2Cl have made these intermediates readily accessible. Among the heterocycles, which can be prepared from these, benzothiadiazinone dioxides of type (1) which are efficient herbicides are particularly interesting.

    4. Irritant and Defense Substances of Higher Plants—A Chemical Herbarium (pages 164–184)

      Prof. Dr. Hermann Schildknecht

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.198101641

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      A chemical defense mechanism has been found in many higher plants which protects them from enemies and harmful influences. An example are the biogenic amines from the stinging hairs of Urticaceae. The “leaf movement factors” (LMF) of legumes e.g. the sensitive plants (Mimosa pudica) release a special type defense mechanism: it feigns death.

  2. Communications

    1. Top of page
    2. Reviews
    3. Communications
    4. Book Reviews
    5. Corrigenda
    1. Lewis Acid Catalyzed Alkylations of CC-Multiple Bonds; Rules for Selective Enlargements of Carbon Skeletons (pages 184–186)

      Dr. Herbert Mayr

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.198101841

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      A preconception or many organic chemists, that cationic CC couplings are difficulty controllable and frequently lead to oligo- and polymeric products, would appear no longer to hold. If a difficultly ionizable product BX is formed from a readily ionizable educt AX in an electrophilic alkylation, then good yields can be achieved.

    2. Reductive Synthesis and Reactivity of Tris(butadiene)molybdenum and -tungsten (pages 186–187)

      Dr. Wolfgang Gausing and Prof. Dr. Günther Wilke

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.198101861

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      A characteristic model for catalytic syntheses of cyclododecatriene (CDT) on transition metals has the reaction sequence shown below. The compound (1), previously obtained only in traces, has now been prepared in 29% yield from MoCl4 2THF, Mg, and THF (butadiene). (2) and (3), the possible intermediates of the reaction (1) [RIGHTWARDS ARROW] CDT, could be isolated.

    3. Synthesis, Isolation, and Identification of Translationally Isomeric [3]Catenanes (pages 187–189)

      Prof. Dr. Gottfried Schill, Dr. Klaus Rissler, Prof. Dr. Hans Fritz and Dr. Walter Vetter

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.198101871

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      A new type of isomerism has been observed in compounds made up of three rings, in which the central ring contains two bulky groups: the lateral rings are either arranged next to each other [Type (1)] or are separated by the bulky groups.

    4. 1,4-Dihydro-1,4-ethenobenzotropylium Tetrafluoroborate; Synthesis and Intramolecular Charge-Transfer Interaction (pages 189–190)

      Prof. Dr. Tomoo Nakazawa, Keiji Kubo and Prof. Dr. Ichiro Murata

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.198101891

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      “Fusion” of barrelene and the tropylium ion in a molecule affords a model system for studies of the intramolecular charge-transfer interactions and interaction between non-bonding π-orbitals in a bicyclo[2.2.2]octane framework. (1) was synthesized in several steps from 1-amino-cycloheptatriazol-6-one and oxepin.

    5. An Onium Anion (pages 190–192)

      Dr. Douglas Lloyd, Dr. Raymond K. Mackie, Dr. Glynis Richardson and Dr. Donald R. Marshall

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.198101901

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      A carbanion, which concomitantly is a part of an onium system, namely an “onium anion” such as(2), could be generated from cations of the dihydrodiazepinium salts, e.g. (1). “Onium anions” can also be postulated as intermediate steps in known reactions.

    6. The Electronic Triplet State of a Peralkylated Cyclobutadiene (pages 192–193)

      Priv.-Doz. Dr. Jakob Wirz, Prof. Dr. Adolf Krebs, Dipl.-Chem. Hermann Schmalstieg and Dr. Herbert Angliker

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.198101921

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      The first experimental data on the energy, geometry, absorption and lifetime of the triplet state of a cyclobutadiene derivative were obtained using (1) as example. The observation of the short-lived triplet state was accomplished by flash-spectroscopic sensitization. The adiabatic and the vertical triplet energy of (1) are estimated to be 50 ± 5 and ⩾ 120 kJ/mol, respectively.

    7. Addition of Carbenes to Reactive Metal-Metal Bonds—A Simple Synthetic Method for μ-Methylene Complexes (pages 193–196)

      Prof. Dr. Wolfgang A. Herrmann, Dipl.-Chem. Christine Bauer, Dr. Johann Plank, Willibald Kalcher, Dipl.-Chem. Dieter Speth and Prof. Dr. Manfred L. Ziegler

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.198101931

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      A general route to μ-methylene complexes (dimetallacyclopropanes) is the addition of carbenes (generated from diazoalkanes) to species with reactive metal-metal bonds. For example, (Me5C5)2Rh2(CO)2 reacts with carbenes RR′C: depending on the spatial requirements of the substituents R and R′ with elimination of CO to give (1) or with intramolecular opening of the carbonyl bridge to give (2).

    8. Tetrafluoroboric Acid-Methanol (1/2), Cyclic Molecules by Hydrogen Bonds between Ions (page 196)

      Prof. Dr. Dietrich Mootz and Dipl.-Chem. Michael Steffen

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.198101961

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      An oxonium salt with the previously unobserved bis(methanol)hydrogen cation [(CH3OH)2H]+ is the HBF4·2CH3OH phase which melts congruently at −41 °C in the system HBF4·CH3OH-CH3OH. The acid proton couples two CH3OH molecules through a very short H-bond. Two of these cations and two BFmath image anions form cyclic dimers having an almost planar O4F2 ring joined by H-bonds.

    9. Elimination and Addition at the Phosphorus-Carbon pπ-pπ Bond (page 197)

      Prof. Dr. Rolf Appel, Prof. Dr. Günther Maier, Dr. Hans Peter Reisenauer and Dipl.-Chem. Axel Westerhaus

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.198101971

      A novel compound with P[TRIPLE BOND]C triple bond, phenylmethylidynephosphane (2), was produced by pyrolysis and trapped at −196 °C. The educt (1) decomposes almost quantitatively into (2) and Me3SiCl in a Hg-diffusion pump vacuum at 700 °C; the educt (3), on the other hand, only yields (2) at 800 °C. Solutions of (2) are stable only at low temperatures; at 0 °C the half-life is 7 min.

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    10. Ba4SiAs4, and Ba4GeAs4, Zintl Phases with Isolated SiAsmath image and GeAsmath image anions (pages 197–198)

      Dr. Brigitte Eisenmann, Dipl.-Ing. Hanna Jordan and Prof. Dr. Herbert Schäfer

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.198101972

      Examples for an extension of the Zintl-Klemm concept to compounds whose anion partial structure is made up of two elements are the newly synthesized isolypic compounds Ba4SiAs4 and Ba4GeAs4. They contain “isolated” SiAs4 -or GeAs4 tetrahedra, i.e. surrounded only by Ba counterions. The title compounds are bridging members between the ternary intermetallic compounds and the salts with complex anions. A principle concerning the charge distribution found in Zintl-phases with complex anions remains valid.

    11. Acenazulenediones: Synthesis, Spectroscopy, Electrochemical Detection of a Double Redox Cycle (pages 198–199)

      Margarete Baier, Prof. Dr. Jörg Daub, Adelheid Hasenhündl, Prof. Dr. Andreas Merz and Dr. Knut M. Rapp

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.198101981

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      The first examples of a previously unknown type of quinone have been synthesized, namely the acenazulenediones (1) and (2); electrochemical studies reveal the merocyanine-character of these species.

    12. 3,3-Diazirinedicarboxylic Acid (“Cyclodiazomalonic Acid”) and Some of Its Derivatives (pages 200–201)

      Dr. Gennady V. Schustov, Nina B. Tavakalyan and Prof. Dr. Remir G. Kostyanovsky

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.198102001

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      Cyclic isomers of diazomalonic acid and its esters, the diazirines (3) and (2) have been prepared 3,3-Diazirinedicarboxylic esters (2) are formed on reaction of the tosyloxyimino compounds (1) with O-alkylhydroxylamine; hydrolysis of (2) yields the free dicarboxylic acid (3). These newly synthesized compounds are of interest as reagents for the preparation of electrophilic cyclopropane derivatives.

    13. Cleavage of a Metal-Metal Bond by 1,3-Butadiene under Photochemical Conditions (pages 201–202)

      Prof. Dr. Cornelius G. Kreiter and Dipl.-Chem. Wolfgang Lipps

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.198102011

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      The unexpected decomposition of Mn2(CO)10 into the ligands Mn(CO)5, Mn(CO)4 (and CO) and formation of a butenylene bridge from butadiene were found on irradiation of Mn2(CO)10 in the presence of butadiene. Besides (1) (yellow platelets, 30% yield), the already known complex (2) (orange needles, 7.4% yield) is also formed. A common intermediate is plausible, but not detectable.

    14. 9,9′-Bianthryl-10,10′-dicarbonitrile, An Aromatic π-System with Six One-electron Redox Steps (pages 202–203)

      Priv.-Doz. Dr. Jürgen Heinze

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.198102021

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      The first aromatic system with more than four reversible one-electron transfer steps, namely the title compound (1), has been investigated. The six redox steps can be detected cyclovol-tammetrically in the total absence of water. The scale extends from the tetraanion to the dication.

    15. Novel Method for the Phase-Transfer Catalyzed Sulfodechlorination of 1-Chloro-2,4-dinitrobenzene (pages 203–204)

      Dipl.-Chem. Markus Gisler and Prof. Dr. Heinrich Zollinger

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.198102031

      Mild conditions and very good yields typify the sulfodechlorination of 1-chloro-2,4-dinitrobenzene with potassium disulfite to 2,4-dinitrobenzoic acid in the presence of protonated tertiary amines as phase-transfer catalysts; the yield and above all the purity of the product depends on the chain-length of the alkyl moiety of the amine.

    16. Trinuclear Clusters from HCo(CO)4 Solutions (pages 204–205)

      Dr. Giuseppe Fachinetti, Laura Balocchi, Dr. Fernando Secco and Dr. Marcella Venturini

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.198102041

      HCo3(CO)9(3)is the first isolable hydrido-carbonyl cluster, which can be obtained using HCo(CO)4(1) as starting compound. The trinuclear, electronically unsaturated cluster is formed by thermal decomposition of (1) together with the expected Co2(CO)8(2). Lower nuclear clusters such as (3) are discussed as catalysts, e.g. in homogeneous hydroformylation or CO reduction.

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    17. Functional Groups at Concave Sites: Asymmetric Diels-Alder Synthesis with Almost Complete (Lewis-Acid Catalyzed) or High (Uncatalyzed) Stereoselectivity (pages 205–207)

      Priv.-Doz. Dr. Günter Helmchen and Dr. Roland Schmierer

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.198102051

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      A new concept for development of reagents for asymmetric syntheses was used as a basis for the synthesis of alcohols (1) and (2). Their fumarates undergo Lewis-acid catalyzed or uncatalyzed addition to anthracene with very good stereo-selectivity; depending on whether a derivative of (1) or (2) is the educt, inverse configurated products are obtained.

    18. Functional Groups at Concave Sites: Asymmetric Alkylation of Esters with Very High Stereoselectivity and Reversal of Configuration by Change of Solvent (pages 207–208)

      Dr. Roland Schmierer, Gregor Grotemeier, Priv.-Doz. Dr. Günter Helmchen and Adel Selim

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.198102071

      An excellent asymmetric induction (enantiomeric excess >90%) is achieved in the α-alkylation of esters of carboxylic acids and the alcohols (1) or (2) (see previous contribution). A drastic solvent effect (THF or THF-HMPT 4:1) enables each of both enantiomers of a compound to be synthesized in high optical purity.

    19. Selective Reduction of the Nitro to the Amino Functional Group by means of the Phthalocyaninecobalt (I) Anion; Synthesis of N-Heterocycles and Alkaloids (pages 208–210)

      Dr. Heiner Eckert

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.198102081

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      Two advantages of the reduction of nitro compounds with the phthalocyanine-cobalt(I) anion ([Co1Pc]) are especially noteworthy: the possibility of converting nitro compounds into N-heterocycles in a one-pot process with reduction and condensation, and the possibility of reducing nitro groups in the presence of many sensitive functional groups without having to protect them. An example is the synthesis of precursors (1) of the anti-tumor agent camptothecine (R3 = H, Cl).

    20. “Magnetochemical Series” for Lanthanoid Compounds (pages 210–211)

      Priv. Doz. Dr. Werner Urland

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.198102101

      “Magnetochcmical series”, not only for ligands but also for central ions, can be drawn up in the case of alkali-metal lanthanoid oxides or halides. To explain the magnetic behavior of these compounds use was made, inter alia, of the Angular Overlap (AO) model. The AO parameter e0(R) could be determined for some series of compounds (from susceptibility measurements). Taking into account the (calculated) overlap integrals Smath image(R) and additional relationships afforded magnetochemical series of the ligands I< Br< Cl< F ≈ O2− and of the lanthanoids. The sequence of the latter series Corresponds to the pattern of lanthanoid contraction.

    21. Conformational Coupling between Ring A and Ring B in Isobacteriochlorins (pages 211–212)

      Dr. Christoph Kratky, Dipl. Naturwiss. EIH Christof Angst and Dr. Jon Eigill Johansen

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.198102111

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      Octaethylisobacteriochlorin and its metal complexes are model substances for sirohy-drochlorin. In the free tetrahydroporphyrin derivative, e.g. (1), the trans vicinal ethyl groups are always arranged diaxially; in the metal compounds, e.g. (2), the nickel(II) ions cause considerable deformation of the whole porphyrin skeleton, such that the diequatorial conformation of the vicinal ethyl groups is energetically favored.

    22. Chalcogenide Iodides of Arsenic (pages 212–214)

      Prof. Dr. Rüdiger Kniep and Dipl.-Chem. Horst Dieter Reski

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.198102121

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      Structural Investigations on α-AsTeI(1)and α-AsSeI(2) and similar compounds has now been possible, since single crystals could be grown in the ternary systems As-(S, Se, Te)-I, which have a strong tendency to form glasses. α-AsTeI (1) proves to have the same double-chain structure as, e.g., SbSI; in α-AsSeI (2) the double chain degenerates to an AsSe spiral with terminal iodine atoms.

    23. Permetalated Methyl Isocyanide (pages 214–215)

      Prof. Dr. Wolf Peter Fehlhammer, Dipl.-Chem. Fritz Degel and Dipl.-Chem. Heribert Stolzenberg

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.198102141

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      The nonacarbonyltricobalt cluster(1), the first of its kind having a functional nitrogen group on the methylidyne C-atom has been synthesized from (CO)5Cr[BOND]CNCCl3 and Co2(CO)8. An X-ray structure analysis is available. The isocyanide (1) opens up a route to further metal-rich CNC-bridged systems.

  3. Book Reviews

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

    1. Top of page
    2. Reviews
    3. Communications
    4. Book Reviews
    5. Corrigenda
    1. You have free access to this content
      Erratum (page 216)

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.198102161