Angewandte Chemie International Edition in English

Cover image for Vol. 16 Issue 11

November 1977

Volume 16, Issue 11

Pages 735–806

Currently known as: Angewandte Chemie International Edition

  1. Reviews

    1. Top of page
    2. Reviews
    3. Communications
    4. Abstracts
    5. Book Reviews
    1. Fluorinated Isocyanates and Their Derivatives as Intermediates for Biologically Active Compounds (pages 735–742)

      Dr. Engelbert Kühle and Dr. Erich Klauke

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.197707353

      Thumbnail image of graphical abstract

      Herbicides, fungicides, and bactericides with favorable toxicological propertiese.g. compounds (1)(3), can be obtained via fluorinated isocyanates which do not have to be isolated.

    2. Synthesis and Reactions of N-Chlorocarbonyl Isocyanate (pages 743–750)

      Dr. Hermann Hagemann

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.197707431

      Thumbnail image of graphical abstract

      N-Chlorocarbonyl isocyanate is a highly reactive derivative of iminodicarboxylic acid. Its two functional groups are accessible to reactions exhibiting overall selectivity; the compound also undergoes cyclization under mild conditions.

    3. Entanglement of Thread Molecules and Its Influence on the Properties of Polymers (pages 751–766)

      Dr. Martin Hoffmann

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.197707511

      In melts and dilute solutions long threadlike molecules exist as a coil. If several coils interpenetrate one chain can wind around another, thus restricting further movement. Entanglement can influence relaxation behavior and, in the case of concentrated polymer solutions, the osmotic pressure as well.

    4. Flexible Drug Molecules and Dynamic Receptors (pages 766–777)

      Prof. Dr. R. J. P. Williams

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.197707661

      Thumbnail image of graphical abstract

      An insight into the mode of action of drugs can be gained by the study of the changes of shape of drug molecules and receptors (proteins, membrances, etc.). The static lock and key model will probably have to be replaced by the concept of dynamic states.

  2. Communications

    1. Top of page
    2. Reviews
    3. Communications
    4. Abstracts
    5. Book Reviews
    1. Simple Synthesis of Racemic Proline (page 777)

      Prof. Dr. Ulrich Schmidt and Dr. Hans Poisel

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.197707771

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      Racemic proline was formerly accessible only by complicated synthetic procedures. A facile preparation affords the amino acid in overall yield of ca. 45% starting from pyrrolidine.

    2. Photochemical [2+2] Cycloaddition between Parallel CC and NN Double Bonds (pages 777–779)

      Dr. Wilfried Berning and Prof. Dr. Siegfried Hünig

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.197707772

      Thumbnail image of graphical abstract

      A [π2s + π2s]-photocyclization between non-activated CC and NN double bonds has been observed for the first time for the rigid molecule (1), which is transformed into a novel cage compound. In other cases this ring closure is precluded by the faster elimination of N2.

    3. A New Synthesis of Pyrimidines and Pyrimidinones (pages 779–780)

      Dr. R. L. N. Harris and Dr. J. L. Huppatz

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.197707791

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      Dichloropyrimidines (3) and suitably substituted chloropyrimidinones(4) can be obtained from the amides (1) and (2) in the presence of POCl3. The yields are highest for R3 = aryl.

    4. A Novel Heteroaromatic System: 2,1,3-Benzothiadiazinylium Derivatives (page 780)

      Dr. habil. Wolfgang Kosbahn and Dr. Helmut Schäfer

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.197707801

      Thumbnail image of graphical abstract

      2,1,3-Benzothiadiazinylium cations of type (1), which have now been synthesized for the first time, formally represent a transition between the purely inorganic cations S4Nmath image, S4Nmath image, S5Nmath image and the organic thiapyrylium cations. The (N-1)[DOUBLE BOND]S bond functions as dienophile.

    5. cis- and trans-Diazene (Diimine) (pages 780–781)

      Prof. Dr. Nils Wiberg, Dr. Gerd Fischer and Dr. Heinz Bachhuber

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.197707802

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      The three isomeric forms of N2H2 have now been detected and characterized. Na, K, and aged Cs tosylhydrazide afford diazene; fresh Cs tosylhydrazide gives isodiazene. According to its IR spectrum diazene contains varying proportions of the cis and trans forms, depending upon the conditions.

    6. α-Oxocarbene-Oxirene Isomerization: Photolysis of [1-13C]-2-Diazo-1-phenyl-1-propanone and [2-13C]-1-Diazo-1-phenyl-2-propanone (pages 781–782)

      Priv.-Doz. Dr. Klaus-Peter Zeller

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.197707811

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      Equilibration between two isomeric oxocarbenes has now been studied quantitatively for the first time starting from both13C-labeled diazoketones. Oxocarbene (1) reacts preferentially via the oxirene (2) to form (3), while (3) undergoes mainly direct Wolff rearrangement to the ketene.

    7. An Imino-Bridged Triaza-λ5-phosphetine (page 783)

      Priv.-Doz. Dr. Edgar Niecke and Hans-Günther Schäfer

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.197707831

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      The first PN bicyclic with a P[DOUBLE BOND]N bond in the ring is formed from the phosphane (1), R = isopropyl, R′ = tert-butyl, and tert-butyl azide. The cycloadduct (2) is crystalline and practically insensitive to atmospheric moisture.

    8. Simple de-novo Synthesis of Reactive Pseudoglycals (Hex-2-enopyranosides)—Stereospecific α-Glycoside Coupling (pages 783–784)

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

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.197707832

      Thumbnail image of graphical abstract

      The unsaturated sugar derivatives(1) and (2), R[DOUBLE BOND]Ac, are readily accessible via the indicated route. (1), R[DOUBLE BOND]Ac, is conveniently transformed by alcohols into the formerly difficultly obtainable α-glycosides so valuable for the synthesis of modified sugars and oligosaccharides.

    9. Azuleno [4,5,6-cd] phenalene; A Novel Nonalternant Isomer of Benzo [a] pyrene (pages 784–785)

      Dr. Kazuhiro Nakasuji, Eishiro Todo and Prof. Dr. Ichiro Murata

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.197707841

      Thumbnail image of graphical abstract

      An insight into the mode of action of the carcinogen benzo [a] pyrene(1) could come from the study of analogous compounds. Azulenophenalene (2), which has now been synthesized, is expected to have a considerable biological activity.

    10. Base-Stabilized Silyleneiron Complexes (pages 785–786)

      Prof. Dr. Günter Schmid and Dipl.-Chem. Eckhard Welz

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.197707851

      Thumbnail image of graphical abstract

      Attempted syntheses of monomeric silylene complexes have so far met with very modest success. The first base-stabilized silyleneiron complexes, e.g. (1), have now been isolated.

    11. New Aliphatic Thioacylating Reagents; Preparation of tert-Butyl Esters of Aliphatic Dithiocarboxylic Acids via Bis(thioacyl) Sulfide (pages 786–787)

      Prof. Dr. Shinzi Kato, Takashi Takagi, Tomonori Katada and Prof. Dr. Masateru Mizuta

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.197707861

      Thumbnail image of graphical abstract

      Aliphatic bis(thioacyl) sulfides(1), now obtainable by routes A and B, are versatile reagents. For example, they can be used to prepare dithio esters, also of sterically hindered alcohols. (1), R = isopropyl, dimerizes to the dithietane derivative (2), which like (1) is possibly an intermediate of the cyclization of dithio acids to hexathiaadamantanes.

    12. 2,4-Diisopropyl-1,3-dithietane-2,4-diyl Bis(dithioisobutyrate), a Dimeric Form of Bis(thioacyl) Sulfide (pages 787–788)

      Prof. Dr. Shinzi Kato, Akira Hori, Takashi Takagi and Prof. Dr. Masateru Mizuta

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.197707871

      Thumbnail image of graphical abstract

      Aliphatic bis(thioacyl) sulfides(1), now obtainable by routes A and B, are versatile reagents. For example, they can be used to prepare dithio esters, also of sterically hindered alcohols. (1), R = isopropyl, dimerizes to the dithietane derivative (2), which like (1) is possibly an intermediate of the cyclization of dithio acids to hexathiaadamantanes.

    13. Dichloro(porphyrinato)molybdenum(IV)—Synthesis and Structure (pages 788–789)

      Dipl.-Ing. Tharcis Diebold, Dr. Bernard Chevrier and Prof. Dr. Raymond Weiss

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.197707881

      Two porphyrinato-molybdenum(IV)compounds without and Mo[DOUBLE BOND]O bond have now been synthesized and thoroughly characterized. The paramagnetic compounds should prove useful starting materials for the synthesis of other porphyrin complexes of low-valent Mo.

    14. Co2(CO)8 Catalyzed Reactions of Cyclic Ethers with Hydrosilanes and Carbon Monoxide (page 789)

      Yoshio Seki, Prof. Dr. Shinji Murai, Iwao Yamamoto and Prof. Dr. Noboru Sonoda

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.197707891

      Thumbnail image of graphical abstract

      Silyl-proctected hydroxy aldehydes are obtainable as shown below. Owing to the occurrence of numerous side reactions, hydroformylation of the cyclic ether is not a suitable method for the synthesis of hydroxy aldehydes.

    15. Tris(tert-butylimino)sulfur(VI) and Bis(tert-butylimino)(silylimino)sulfur(VI); The “Y-triene” Structure (pages 789–790)

      Prof. Dr. Oskar Glemser, Dr. Siegfried Pohl, Dipl.-Chem. Frank-M. Tesky and Priv.-Doz. Dr. Rüdiger Mews

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.197707892

      Thumbnail image of graphical abstract

      “Y-trienes”, compounds of threefold coordinated sulfur(CVI), have so far been reported only rarely. It has now been found that not only the trimethylsilyl group but also the tert-butyl group stabilizes the coordination number 3. In solid (2) the SN3, skeleton is planar.

    16. Infrared Rotatory Dispersion of Liquid-Crystalline Solutions of Chiral Molecules (pages 790–791)

      Dr. Ernst-Heiner Korte, Prof. Dr. Bernhard Schrader, Dr. Sauvarop Bualek and Dr. Hans Jürgen Krabbe

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.197707901

      Thumbnail image of graphical abstract

      The absolute configuration of molecules with a chiral center can be established by a new empirical procedure: nematic phases of liquid-crystalline compounds become cholesteric on dissolution of a chiral “guest substance”. The sign of the measured Reflection Cotton Effect provides information whether the three ligands of greatest priority a > b > c (see priority scheme) are arranged clockwise or counterclockwise.

    17. Relationship between the Infrared Rotatory Dispersion of Liquid-Crystalline Solutions of Chiral Molecules and Their Absolute Configuration (pages 791–792)

      Dr. Hans Jürgen Krabbe, Dipl.-Chem. Heinrich Heggemeier, Prof. Dr. Bernhard Schrader and Dr. Ernst-Heiner Korte

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.197707911

      Thumbnail image of graphical abstract

      The absolute configuration of molecules with a chiral center can be established by a new empirical procedure: nematic phases of liquid-crystalline compounds become cholesteric on dissolution of a chiral “guest substance”. The sign of the measured Reflection Cotton Effect provides information whether the three ligands of greates priority a > b > c (see priority scheme) are arranged clockwise or counterclockwise.

    18. Dimeric Bis(di-tert-butylphosphino)stannanediyl: A Cyclic Phosphorus-Tin Ylide (pages 792–793)

      Dr. Wolf-Walther du Mont and Dr. Heinz-Jürgen Kroth

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.197707921

      Thumbnail image of graphical abstract

      The tin compound (tBu2P)2Sn, which is analogous to a carbene, is the first stannylene to be substituted only by R2P groups and also the first kinetically stable P—Sn ylide. Dimers (1) are present in benzene (red solution) (R [DOUBLE BOND] tBu).

    19. A Novel Transformation of Diphenylcyclopropenone: Double Bond Cleavage in the Reaction with Platinum Complexes (pages 793–794)

      Dr. W. Eamon Carrol, Dr. Michael Green, Dr. Judith A. K. Howard, Dr. Michel Pfeffer and Prof. Dr. F. Gordon A. Stone

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.197707931

      The novel dinuclear platinum complex(1) is doubly bridged by ring-opened diphenylcyclopropenone. Neither the cleavage of the CC double bond of a small ring by a transition metal complex nor bridging ligands of this kind (X-ray structure analysis) were formerly known.

      • equation image
    20. An Unusually Facile Electrophilic Substitution at the Cyclopentadienyl Ring in a Half-Sandwich Complex (pages 794–795)

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

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.197707941

      Thumbnail image of graphical abstract

      The mechanism of electrophilic substitution in η-cyclopentadienyl-metal complexes is a controversial topic. The reaction sequence shown below has now been confirmed for the half-sandwich complex C5H5Co(PMe3)2.

    21. Detection of Rigid Rotamers in Disubstituted Cyclopentadienylcobalt Complexes (pages 795–797)

      Dipl.-Chem. Werner Hofmann, Dr. Wolfgang Buchner and Prof. Dr. Helmut Werner

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.197707951

      Thumbnail image of graphical abstract

      Rotation of the cyclopentadienyl ring about the metal-ring bond in complexes such as (1) depends upon the substituents R and R′. The first rigid rotamers of this kind have been detected in (1a), R[DOUBLE BOND]R′[DOUBLE BOND]tBu; (1b), R[DOUBLE BOND]R′[DOUBLE BOND]iPr, exhibits free rotation probably as a result of a “gear mechanism”.

    22. Synthesis of Bridged 1,3,2λ3,4λ3-Diazadiphosphetidines (pages 797–798)

      Dr. Rodney Keat and David G. Thompson

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.197707971

      Thumbnail image of graphical abstract

      The geometrical isomers of PN four-membered ring derivatives, e.g. (MeO—PN—tBu)2, are characterized by exceptionally large differences in their 31P-NMR shifts. In connection with attempts to establish the reason for these differences the novel heterocycles (1) and (2), n = 2 or 3, have now been synthesized.

    23. Structure of Two Highly Strained Tetracyclododecanes (pages 798–799)

      Dr. Otto Ermer

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.197707981

      Thumbnail image of graphical abstract

      The results of crystal structure analysis and force field calculation are compared for two polycylic hydrocarbons. The two isomers (1) and (2) show extreme bond angles and vibrational frequnecies arising from strong H…H repulsions.

    24. Diastereoisomeric [3.3]Paracyclophane Quinhydrones (pages 799–801)

      Prof. Dr. Heinz A. Staab and Dr. Claus P. Herz

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.197707991

      Thumbnail image of graphical abstract

      Models suitable for the intramolecular simulation of normal charge-transfer interactions are the donor-acceptor cyclophanes of the [3.3] paracyclophane series. The diastereomeric [3.3] paracyclophane quinhydrones (1) and (2) have now been synthesized and characterized as the first compounds of their kind.

    25. Indirectly Transmitted Charge-Transfer Interactions: Multilayered [2.2] Paracyclophane Quinhydrones (pages 801–803)

      Prof. Dr. Heinz A. Staab, Dipl.-Chem. Udo Zapf and Anneliese Gurke

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.197708011

      Thumbnail image of graphical abstract

      [2.2] Paracyclophane quinhydrones with intercalated benzene rings have now been synthesized for the first time in the form of their methyl ethers (1) and (2). Their broad CT band must be due to an intramolecular CT transition; the charge is transmitted in “vertical conjugation” through the π-electron system of the benzene. Orientation dependence of the CT absorption as observed in simple donor-acceptor 2.2 paracyclophanes is almost completely absent.

  3. Abstracts

    1. Top of page
    2. Reviews
    3. Communications
    4. Abstracts
    5. Book Reviews
    1. ABSTRACTS (pages 803–804)

      Version of Record online: 22 DEC 2003 | DOI: 10.1002/anie.197708031

  4. Book Reviews

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

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