Angewandte Chemie International Edition in English

Cover image for Vol. 19 Issue 2

February 1980

Volume 19, Issue 2

Pages 79–150

Currently known as: Angewandte Chemie International Edition

    1. Cover Picture (Angew. Chem. Int. Ed. Engl. 2/1980)

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.198000791

    2. Graphical Abstract (Angew. Chem. Int. Ed. Engl. 2/1980)

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.198000792

  1. Reviews

    1. Top of page
    2. Reviews
    3. Communications
    4. Book Reviews
    1. Raw Material-Polymer Interrelationships — Today and Tomorrow (pages 79–87)

      Prof. Dr. Klaus Weissermel

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.198000793

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      Petroleum, natural gas, and coal are presently employed not only as raw materials but primarily as sources of energy. One of the most pressing needs is to disengage this double function and to better utilize fossil resources. Possible solutions are demonstrated by means of plastics (a breakdown of oil consumption in the Federal Republic of Germany in 1976 is shown on the right).

    2. Chemistry and Function of Human Plasma Proteins (pages 87–99)

      Prof. Dr. Hans-Gerhard Schwick and Heinz Haupt

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.198000871

      Components of the blood clotting system, immunoglobulins, lipoproteins, and numerous other proteins—numbering over 100—have been isolated from blood plasma by new techniques. Some of the biologically active proteins obtainable in this way possess considerable prophylactic and therapeutic potential. In fact, blood plasma would appear too valuable for mere transfusion.

    3. New Technologies for the Filmless Manufacture of Printing Forms (pages 99–110)

      Dr. Hansjörg W. Vollmann

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.198000991

      The innovative pressure exerted by electronics on the processing of optical information poses the chemist new tasks: apart from the chemical properties of materials, their electrical properties are becoming increasingly important. Chemicals suitable for production of reprographic forms by electrophotography without film include CdS, ZnO, and organic heterocycles such as oxazoles and benzothiazoles.

    4. On the Symbolic Language of the Chemist (pages 110–125)

      Prof. Dr. Rudolf Hoppe

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.198001101

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      In a stoke of genius, Berzelius created the formula language of chemistry over 100 years ago. This language has hardly changed since then. However, it is just not informatic enough to deal with inorganic solid state compounds, and more recent proposals also appear rather inadequate. The article closes with a call for a new Berzelius.

  2. Communications

    1. Top of page
    2. Reviews
    3. Communications
    4. Book Reviews
    1. Synthesis and Crystal Structure Analysis of Decathiacyclotetradecane-6,7,13,14-tetraone, S10(CO)4 (pages 125–126)

      Prof. Dr. Herbert W. Roesky, Dr. Hamid Zamankhan, Dr. Jan Willem Bats and Prof. Dr. Hartmut Fuess

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.198001251

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      The first 14-membered ring found in sulfur chemistry is present in S10(CO)4(1). This compound is stable at room temperature; it forms yellow crystals and exists in the expected conformation.

    2. 1,4-Dioxanes with Four Fluorine and/or Trifluoromethyl Substituents on C2 and C3 from Vicinal Perfluorodicarbonyl Compounds (page 126)

      Dr. Werner Schwertfeger and Dr. Günter Siegemund

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.198001261

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      1,4-Dioxanes perfluorinated at C2 and C3 of type (4) are accessible from dicarbonyl compounds (1), ethylene dimesylate (3), and KF (1:1:2). The synthesis can be generalized (M = methanesulfonyl; Rf, R′f = F, CF3).

    3. A Selective Pathway from Methanol to Ethylene and Propene (pages 126–127)

      Dr. Friedrich August Wunder and Dr. Ernst Ingo Leupold

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.198001262

      Assured supplies of raw materials is of topical interest in view of the threatening scarcity of petroleum. Mu-doped aluminosilicate catalysts transform methanol into a surprisingly narrow range of products containing a large proportion of ethylene and propene. Methanol is accessible, in principle, from all carbonaceous materials via synthesis gas.

    4. Addition of Alkanethiols to Diketene (pages 127–128)

      Dr. Ulrich Hertenstein

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.198001271

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      Reactions of RSH with diketene(1) are highly dependent upon the reaction conditions. Acid-catalyzed reaction of alkanethiols with (1) leads, like the photo or radical reaction, to the lactone (2). This could not be deduced from previous findings. (2) reacts with alcohols to give γ-(alkylthio)crotonic esters.

    5. Direct Synthesis of the Perfluoroalkanesulfinates of Iron(II), Cobalt(II), and Nickel(II): SO2-Assisted Addition of Alkyl Halides to Transition Metals (pages 128–129)

      Dr. Konrad von Werner and Hermann Blank

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.198001281

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      Reactions of typical transition metals with alkyl halides normally take place only after prior chemical or physical activation of the metals. It is now possible to bring about reaction of commercial grade Fe, Co, and Ni powder with perfluoroalkyl iodides (R[BOND]I) under mild conditions: In the presence of SO2, the alkanesulfinates (1) with a dinuclear cation are formed in dimethylformamide at room temperature.

    6. Pyrrolizidines by Rearrangement of β-Lactams (pages 129–130)

      Dr. Friedrich Cavagna, Dr. Adolf Linkies, Dr. Hartmut Pietsch and Dr. Dieter Reuschling

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.198001291

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      1,5,5-Trifunctionalized pyrrolizidines are formed via ring expansion from the β-lactam (1) in the presence of NaOCH3. The action of acids produces the salt (2). Sterically uniform 1,5-pyrrolizidinedicarboxylic acid can be obtained from the ester (3).

    7. Syntheses with Cyanogen—A Simple Route to 4,5-Dichloroimidazoles (pages 130–131)

      Dr. Dieter Günther and Dr. Dieter Bosse

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.198001301

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      4,5-Dichlorinated imidazoles (1) having an unsubstituted N atom were not previously accessible by a general synthesis. It has now proved possible to produce numerous derivatives (1) in useful yields by synthesis from aldehydes, cyanogen, and hydrogen chloride, thus permitting a study of their reactions.

    8. Functionalization of α-Methylene Ketones (page 131)

      Dr. Jürgen Sander and Dr. Karl Clauss

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.198001311

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      β-Substituted acrylonitriles (4) and (5) are formed in a novel reaction from the oxathiazine derivatives (3) via ring opening and elimination of SO3. The reactants (3) are in turn accessible in several steps from the ketones (1) having an α-CH2 group. Step (2) [RIGHTWARDS ARROW] (3) is also new.

    9. Synthesis and Structure of 3-Chloro-4-hydroxy- and 3,4-epoxyphospholane 1-Oxides (pages 132–133)

      Dr. Friedrich Cavagna, Dr. Utz-Hellmuth Felcht and Dr. Erich F. Paulus

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.198001321

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      Epoxidation of phospholene oxides(1) to give (2) proceeds almost quantitatively by the route shown below, thus superseding previous methods. There is no need to isolate the intermediate (2). An X-ray structure analysis has been performed on one of the stereoisomers of (2a), R1 = OCH3, R2 = R3 = CH3.

    10. New Peptide Synthesis (pages 133–134)

      Dr. Hans Wissmann and Dr. Hanss-Jerg Kleiner

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.198001331

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      Alkylphosphonic anhydrides such as (1) are recommended as condensation reagents for peptide synthesis. One advantage of (1) over dicyclohexylcarbodiimide (DCC) is that no sparingly soluble secondary products are formed. With regard to yield and degree of racemization, the new method is just as good as improved DCC techniques, and in some cases superior.

    11. Stereocontrolled Intramolecular Diels-Alder Reaction of Heterodienes; Studies on the Synthesis of Cannabinoids (pages 134–135)

      Prof. Dr. Lutz-F. Tietze, Dipl.-Chem. Günter von Kiedrowski, Klaus Harms, Dr. William Clegg and Prof. Dr. George Sheldrick

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.198001341

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      The skeleton (4) of tetrahydrocannabinol having translinked rings A and B can be obtained optically pure from the diketone (1) and (R)-citronellal (2). The key step is intramolecular Diels-Alder reaction (up to 20°C!) of the heterodiene intermediate (3).—Derivatives of (4) are of interest, e.g., in the treatment of glaucoma.

    12. (3R,S)-3,4-Dicarboxy-3-hydroxybutyl Coenzyme A, an Inhibitor of the Citrate Synthase Reaction (page 136)

      Prof. Dr. Hermann Eggerer, Dipl.-Chem. Walter Giesemann and Horst Aigner

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.198001361

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      Citrate synthase, an enzyme of the tricarboxylic acid cycle, catalyzes the formation of citrate and coenzyme A from acetyl CoA and oxalacetate. In order to establish whether citryl CoA is formed as a true intermediate on the synthase, the analogue (1), R1 = CH2SCoA, R2 = H, has been synthesized (citryl CoA contains CO in place of CH2). Kinetic measurements showed that (1) acts as a strong inhibitor.

    13. Tetrakis(phenylimino)cyclobutane (Tetrameric Phenyl Isocyanide) (pages 136–137)

      Prof. Dr. Hans Jürgen Bestmann, Dr. Günter Schmid and Dr. Eberhard Wilhelm

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.198001362

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      A nitrogen analogue of the hitherto unknown cyclobutane tetraone, the title compound (2), is formed as red-violet crystals from the phosphorane (1) and nitrobenzene in a one-pot reaction. The arrangement of phenyl groups indicated in the formula is confirmed by X-ray structure analysis. (2) is reduced, e.g. by phenylhydrazine, to (3), the first amidine of squaric acid whose N atoms are not linked in a ring.

    14. β-Azolyl-α,α-dicarbonyl Compounds (pages 137–138)

      Dr. Thomas Maier and Dr. Hilmar Mildenberger

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.198001371

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      Triazole derivatives (3) having a fungicidal action have been prepared by addition of triazole (2) to the α,β-unsaturated dicarbonyl compounds (1). The corresponding pyrazole derivatives are ineffective.

    15. Tetrachlorovinylcarbene from Tetrachlorocyclopropene; Facile Synthesis of Vinylcyclopropanes (pages 138–140)

      Dipl.-Chem. Walter Weber and Prof. Dr. Armin de Meijere

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.198001381

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      Tetrachlorovinylcarbene, Cl[BOND][BOND]CCl[DOUBLE BOND]CCl2, is unexpectedly formed on reaction of tetrachlorocyclopropene (1) with alkenes (2), in which the adducts (3) can be isolated. As shown by numerous examples, this type of reaction can be generalized, e.g. for synthesis of acids and esters (3), R1 = CO2H and CO2R, having potential as insecticides.

    16. Mutual Interconversion of the Chromophoric Systems of Porphyrinogen and Isobacteriochlorin (pages 140–141)

      dipl. Naturwiss. ETH Christof Angst, Dr. Masahiro Kajiwara, Dr. Engelbert Zass and Prof. Dr. Albert Eschenmoser

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.198001401

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      Reactions of hexahydroporphyrins in the absence of air are strongly influenced by metal ions. Thus the tetrapyrrolic porphyrinogen (1), R = C2H5, reacts in the presence of Co2+via several steps, including isobacteriochlorins (2), to give the hemicorrinoid dipyrrolic compounds (3). These are tautomers of (1). In the presence of Ni2+, (1) form complexes of the new hemicorrinoid-pyrromethenic system (4). ttct-(4) and tttt-(4) were characterized by their spectra and also by X-ray structure analysis. (The species ttt-(2), ttt-(3), and tttt-(4) likewise formed are not included in the scheme below.)

    17. 1,2,3,7,8,20-Hexahydroporphyrin, an Easily Formed Ligand System Isomeric to Porphyrinogens (pages 141–143)

      Dr. Jon Eigill Johansen, dipl.-Naturwiss. ETH Christof Angst, Dr. Christoph Kratky and Prof. Dr. Albert Eschenmoser

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.198001411

      Thumbnail image of graphical abstract

      Reactions of hexahydroporphyrins in the absence of air are strongly influenced by metal ions. Thus the tetrapyrrolic porphyrinogen (1), R = C2H5, reacts in the presence of Co2+via several steps, including isobacteriochlorins (2), to give the hemicorrinoid dipyrrolic compounds (3). These are tautomers of (1). In the presence of Ni2+, (1) form complexes of the new hemicorrinoid-pyrromethenic system (4). ttct-(4) and tttt-(4) were characterized by their spectra and also by X-ray structure analysis. (The species ttt-(2), ttt-(3), and tttt-(4) likewise formed are not included in the scheme below.)

    18. Synthesis and Transformations of 5-Cyano-2,2,8,8,12,13,17,18-octamethylisobacteriochlorin (pages 143–145)

      Dr. Paul Naab, dipl.-Chem. ETH René Lattmann, dipl.-Naturwiss. ETH Christof Angst and Prof. Dr. Albert Eschenmoser

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.198001431

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      A model substrate for studies in the hexahydroporphyrin series, i.e. the title compound (1) having C2v symmetry, has been prepared by a multistep de-novo synthesis from a cyanosubstituted thiolactam. Catalytic hydrogenation of (1) affords the highly O2-sensitive 2,3,7,8,15,24-hexahydro derivative; attempts to incorporate metal ions into this species lead to complexes of the 1,2,3,7,8,20-hexahydro isomer.

    19. Tetraphenylcyclobutadienecycloalkenenickel(0) Complexes (pages 145–146)

      Prof. Dr. Heinz Hoberg and Dipl.-Chem. Christian Fröhlich

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.198001451

      Nickel(0) complexes having only one tetraphenylcyclobutadiene ligand (Ph4C4) and one cycloalkene ligand (L) are accessible with surprising ease, e.g. by prolonged stirring of the reagents given below in either at −50°C. (1a) and (1b), green crystals, only decompose at 220 and 260°C, respectively. [(1a), L = 1,5-cyclooctadiene; (1b), L = cyclooctatetraene.]

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    20. Photochemically Induced 1,2-Bis(dialkylalumination) of Diphenylacetylene (page 146)

      Prof. Dr. Heinz Hoberg and Dr. Fernando Aznar

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.198001461

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      The 1,2-addition of R2Al groups to diphenylacetylene can also be accomplished as a photoreaction. Depending upon R and the temperature, trialkylaluminum compounds (R3Al)n and Ph2C2 afford the heterocycle (2) [via (1)] and/or the trans-adduct (3). The photoisomerization (3) [RIGHTWARDS ARROW] (1) does not occur.

    21. Heterogeneously Catalyzed Gas-Phase Bromination of Trifluoromethane (pages 147–148)

      Prof. Dr. Hans Bock, Dipl.-Chem. Jan Mintzer, Dipl.-Chem. Jörg Wittmann and Dr. Jürgen Russow

      Article first published online: 22 DEC 2003 | DOI: 10.1002/anie.198001471

      The optimization of a heterogeneously catalyzed gas-phase reaction by PE spectroscopy is demonstrated for the production of F3CBr, an extinguishing agent used in automatic fire extinguishing installations. A specially developed (PE spectroscopic) gas-analysis technique permits screening of catalysts (and conditions). The best results were obtained with FeCl3/KBr/activated charcoal.

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  3. Book Reviews

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

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