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Angewandte Chemie International Edition
Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
Editor: Peter Gölitz, Deputy Editors: Neville Compton, Haymo Ross
Online ISSN: 1521-3773
Associated Title(s): Angewandte Chemie, Chemistry - A European Journal, Chemistry – An Asian Journal, Zeitschrift für Chemie
Flashback: 50 Years Ago
Angewandte Chemie International Edition was first published in 1962, the mother journal first in 1888. In this monthly flashback, we feature some of the articles that appeared 50 years ago. This look back can open our eyes, stimulate discussion, or even raise a smile.
Archive: 2012
- 50 Years Ago ...
Angew. Chem. Int. Ed. 2013, 52, No. 19, 4970Fluorination was already popular 50 years ago, and two Communications on this topic were published in the same issue. P. Sartori discussed how the electrofluorination of gases that are insoluble in liquid HF could be achieved at atmospheric pressure by forcing the gases through the electrolyte from below. Propane, ethane, methane, and hydrogen sulfide were all electrofluorinated by using this procedure to give mixtures of products. Oskar Glemser, Herbert Roesky, and Karl-Heinz Hellberg reported the reaction of chromium powder with elemental fluorine at high temperature and pressure to produce chromium(V) fluoride and chromium(VI) fluoride as bright-red and lemon-yellow solids, respectively. The compositions of the solids were determined by analyzing the products resulting from hydrolysis. Roesky is in the top two authors who have published the most manuscripts in Angewandte Chemie from 1946–2012 (see the recent Review by François Diederich: Angew. Chem. Int. Ed. 2013, 52, 2714).
The Reviews section contained contributions by Herrmann Schmalzried on solid-state reactions between ionic crystals, including oxides, halides, and sulfides, and by Fritz Kröhnke on synthesis using pyridinium salts. The electronic properties of pyridinium cations make them ideal for use in a range of syntheses, including those of quinolizine rings, indole-3-carboxylic acids, and triarylpyrimidines.
- 50 Years Ago ...
Angew. Chem. Int. Ed. 2013, 52, No. 13, 3550Shock waves and detonations were the subject of a Review by W. Jost and T Just. These methods were used to achieve high temperatures and thus permit the kinetic investigation of fast reactions in the gas phase.
Albert Eschenmoser and co-workers reported the esterification of carboxylic acids with aminoacetals of N,N-dimethylformamide. A range of amino acid and peptide derivatives were studied and the reaction was assumed to proceed by alkylation of the carboxylate oxygen atom. Eschenmoser later published two comprehensive Reviews in Angewandte Chemie on the origin of biomolecular structures, including Vitamin B12 and nucleic acids (see Angew. Chem. Int. Ed. 1988, 27, 5 and Angew. Chem. Int. Ed. 2011, 50, 12 412).
NMR spectroscopy was used by Heinz A. Staab and co-workers to investigate the tautomeric forms of 4 (or 5)-substituted imidazoles. The magnitude of the spin–spin coupling constants of deuterated compounds showed that they exist predominantly in one form. Staab was for many years Director at the Max Planck Institute for Medical Research in Heidelberg, and pioneered the synthesis of rigid phenylacetylene-based macrocycles and cyclophanes (see his recent Obituary: Angew. Chem. Int. Ed. 2012, 51, 12 404).
- 50 Years Ago ...
Angew. Chem. Int. Ed. 2013, 52, No. 09, 2390In the first Review of this issue, Günther Wilke described the cyclooligomerization of butadiene using Ziegler-type catalysts, and transition-metal complexes of the resulting products. Wilke was Director of the Max Planck Institute for Coal Research from 1967–1992, and was in fact Ziegler’s successor in this post.
The reaction between pentafluorosulfurchloride and amines was reported in a Communication by Bernard Cohen and Alan G. MacDiarmid. The resulting adducts were shown to decompose to produce sulfur tetrafluoride, which then reacts further with the amine. MacDiarmid shared the Nobel Prize for Chemistry in 2000 with Hideki Shirakawa and Alan J. Heeger for their work on conductive polymers. A Communication by Heeger on solar cells with a graphene oxide electron-transport layer will be published in Issue 10/2013 to coincide with our 125th Anniversary Symposium.
Reinhard W. Hoffmann reported how the base-catalyzed fragmentation of azobromobezene derivatives can be used to generate the o-bromophenyl anion, which is an intermediate in the formation of benzyne. Hoffmann’s account of the changes in natural product synthesis over time was published in our Jubilee Issue 1/2013.
- 50 Years Ago ...
Angew. Chem. Int. Ed. 2013, 52, No. 05, 1350NMR spectroscopy was already starting to revolutionize organic chemistry, and the applications of NMR to organic chemistry was the subject of a Review by J. D. Roberts, a true hero of physical organic chemistry from Caltech. As well as an introduction to the technique and to topics such as chemical shift and spin–spin coupling, several examples that have become standard textbook knowledge, such as the analysis of the interconversion of chair forms, were given. The author’s prediction of a bright future for NMR was certainly not understated!
The rising popularity of organometallic chemistry was reflected in two articles by E. O. Fischer, who received the Nobel Prize in Chemistry in 1973. In a Review, he discussed the chemistry of metal π complexes with di- and oligo-olefinic ligands, and in a Communication, he reported the expansion of six-membered rings in metal π complexes.
Hubert Schmidbaur, former Chairman of the Editorial Board of Angewandte Chemie, reported the formation of heterosiliconate anions containing organic groups. These anions correspond to the structural units of polymeric feldspars. The ionic structure of the compounds [Me4Sb][Al(OsiMe3)4] was confirmed by NMR spectroscopy and X-ray structural analysis.
- 50 Years Ago ...
Angew. Chem. Int. Ed. 2013, 52, No. 01, 32The first issue of the year started with a Review by the late Emanuel Vogel on valence isomerization in compounds with strained rings. These rearrangement reactions are driven mostly by relief of strain in energy-rich small or medium-sized rings. Vogel’s many achievements are recorded in a personal account of his research career spanning 50 years (Angew. Chem. Int. Ed. 2011, 50, 4278).
A Review by J. Heyna from the former company Hoechst AG on the topic of reactive dyes summarized recent progress on dyes that contain vinylsulfonylgroups and react with nitrogeneous and cellulose fibers. At that time, high-resolution color photography was not available and so the best way to show the results was to produce an insert bearing samples of dyed fabrics. The colors have still not faded!
The preparation of cyclopentadienylcycloheptatrienylchromium(0) was reported by E. O. Fischer and S. Breitschaft. The complex, which was air-sensitive and formed blue solutions in organic solvents, was prepared by reduction of the corresponding chromium(I) cation. Fischer was one of the pioneers of organometallic chemistry and won the Nobel Prize in Chemistry in 1973 for his work on sandwich compounds (see Angew. Chem. Int. Ed. 2011, 51, 6052 for a recent Essay by H. Werner on the subject).
A Journal of the Gesellschaft Deutscher Chemiker
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