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  • Chemistry  (11)
  • STRUCTURAL MECHANICS  (1)
  • 2020-2022
  • 1980-1984  (12)
  • 1950-1954
  • 1981  (12)
  • 1
    Electronic Resource
    Electronic Resource
    Herstellung von 1, 3-Diketonen und von Nitro-diketonen durch (1:1)-Acylierungen von Lithiumenolaten mit Acylchloriden (1981)
    New York, NY : Wiley-Blackwell
    Helvetica Chimica Acta 64 (1981), S. 716-735 
    Details
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Preparation of 1,3-Diketones and of Nitro-diketones by (1:1)-Acylation of Lithium Enolates with Acyl ChloridesSlow addition of precooled solutions of lithium enolates in THF (Fig. 1) to solutions of equimolar amounts of acyl chlorides in the same solvent at temperatures between - 80 and - 100° furnishes 1, 3-diketones in acceptable to good yields (Tables 1-3). Even 3-nitropropionyl and 4-nitrobutyryl chloride can be employed for the (1:1)-acylation of enolates to give the synthetically useful 5- and 6-nitro-1, 3-diketones 13 and 25, respectively. The scope and the limitations of this method of preparing 1, 3-diketones are given and are compared with alternative methods.
    Additional Material: 1 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/hlca.19810640313
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  • 2
    Electronic Resource
    Electronic Resource
    Improved Nitroaldol Reactions and Reductive Routes to Vicinal AminoalcoholsDedicated to Prof. Vladimir Prelog on the occasion of his 75th birthday (1981)
    New York, NY : Wiley-Blackwell
    Helvetica Chimica Acta 64 (1981), S. 2264-2271 
    Details
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Regioselective and flexible procedures are described for the preparation of a variety of protected vicinal nitroalcohols 1, 3 and 5 (see Scheme 5), as is an efficient method for their reduction to the corresponding vicinal aminoalcohols 2, 4 and 6.
    Additional Material: 1 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/hlca.19810640732
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  • 3
    Electronic Resource
    Electronic Resource
    Cyclisch gekreuzt-konjugierte Bindungssysteme, 371) Das vinyloge Sesquifulvalen (1981)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 114 (1981), S. 1679-1696 
    Details
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Cyclic Cross-Conjugated Bond Systems, 371) The Vinylogous SesquifulvaleneAs a model study the tricycloheptenone 8 (“masked tropone”) - obtained from quadricyclanone 7 - is used for the synthesis of the tricyclic fulvene 9, which upon Ag⊕-catalysis or upon direct irradiation is quantitatively isomerized to the highly reactive sesquifulvalene 2. Applying the same scheme to the synthesis of the vinylogous sesquifulvalene 5, the tricyclic aldehyde 16 serves as precursor for the tricyclic fulvene 17, isomeric with 5. 17 is uniformly transformed into 5 in the presence of Ag⊕. The isomeric fulvenes 25 and 26 are exclude as precursors of 5. contrary to literature reports 5 is also obtained from 8-formylheptafulvene but only in very limited yield (max. 10%). 5 can be isolated in crystalline form and shows typical fulvalene-type spectral behavior.
    Notes: In einer Modellstudie wird aus dem Tricycloheptenon 8 (“maskiertes Tropon”) - erhältlich aus Quadricyclanon 7 - das tricyclische Fulven 9 hergestellt, welches unter Ag⊕-Katalyse bzw. unter direkter Belichtung einheitlich zum hochreaktiven Sesquifulvalen 2 isomerisiert. In einem analog konzipierten Zugang zum vinylogen Sesquifulvalen 5 dient der tricyclische Aldehyd 16 als Vor stufe für das mit 5 isomere tricyclische Fulven 17. Die Ag⊕-katalysierte isomerisierung liefert einheitlich 5. Die mit 17 isomeren Fulvene 25 und 26 kommen als Vorstufen für 5 nicht in Frage. In mäßiger Ausbeute (max. 10%) ist 5 entgegen Literaturhinweisen auch aus dem Formylheptafulven 23 erhältlich. Das kristallisiert isolierbare 5 ist durch die Spektren als typisches Fulvalen ausgewiesen.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/cber.19811140510
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  • 4
    Electronic Resource
    Electronic Resource
    Hydridoiridium (III)-Komplexe mit endständigem und verbrückendem Thio- und Selenocyanat1) (1981)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 114 (1981), S. 2360-2364 
    Details
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Hydridoiridium(III) Complexes with Terminal and Bridging Thio- and Selenocyanate1)The thio- and selenocyanato complexes (Ph3P)2(CO)(Cl)(H)IrX 1 (X = SCN) and 2 (X = SeCN) and 2 (X = SeCN) have been prepared from the corresponding tetrafluoroborato- and trifluoromethanesulfonato-compounds (X = BF4, CF3SO3). The SCN ligand in 1 is S-bonded. 2 was obtained as a mixture of linkage isomers. The reaction of 2 with the tetrafluoroborato-complex (Ph3P)2(CO)(Cl)(H)IrFBF3 gives the salt [(Ph3P)2(OC)(Cl)(H)Ir—SeCN—Ir(H)(Cl)(CO)(PPh3)2]+BF-4 which contains the selenocyanate-bridged cation as a mixture of stereoisomers.
    Additional Material: 2 Tab.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/cber.19811140633
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  • 5
    Electronic Resource
    Electronic Resource
    Darstellung und Reaktionen von kationischen Chlorobis(phosphan)platin(II)-Komplexen (1981)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 114 (1981), S. 2971-2978 
    Details
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Preparation and Reactions of Cationic Chlorobis(phosphane)platinum(II) Complexes[(R3P)2Pt(Cl)H2O]+BF-4 (1) and (R3P)2Pt(Cl)OSO2CF3 (2) have been prepared by abstraction of chloride from cis-(R3P)2PtCl2 using tetrafluoroboric acid or trifluoromethanesulfonic acid, respectively. The protons of the aqua ligand in 1 form hydrogen bridges to the BF-4 anion. The acidic complexes 1 and 2 are useful starting materials for new platinum(II) complexes. HCO-3 neutralizes 1 to form the carbonato complex (Et3P)2PtO2CO (5). The heterogenous reaction of 2a with glycinate gives the cationic chelate complex (6). The coordinated water of 1 is easily substituted by other ligands, e. g. phosphanes. The chloro-bridged complexes [(R3P)2PtCl2Pt(PR3)2]2+ are formed by treatment of 1 or 2 with ethers.
    Notes: [(R3P)2Pt(Cl)H2O]+BF-4 (1) und (R3P)2Pt(Cl)OSO2CF3 (2) (R = Et, n-Bu, Ph; 2 PR3 = Ph2PCH2CH2PPh2) werden durch Chlorid-Abstraktion aus cis-(R3P)2PtCl2 mit Tetrafluoroborsäure bzw. Trifluormethansulfonsäure erhalten. Die Protonen des Aqua-Liganden von 1 bilden Wasserstoffbrücken zum BF-4-Anion aus. Die sauren Komplexe 1 und 2 lassen sich zur gezielten Synthese neuer Platin(II)-Komplexe nutzen. In heterogener Reaktion entsteht aus 2a mit Glycinat der kationische Chelatkomplex (6). Hydrogencarbonat neutralisiert 1 unter Bildung des Carbonatokomplexes (Et3P)2PtO2CO (5). Das koordinierte H2O in 1 läßt sich leicht durch andere Liganden, z. B. Phosphane, ersetzen. 1 und 2 bilden in Ethern die Chloro-verbrückten Dikationen [R3P)2PtCl2Pt(PR3)2]2+.
    Additional Material: 2 Tab.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/cber.19811140906
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  • 6
    Electronic Resource
    Electronic Resource
    Cyclisch gekreuzt-konjugierte Bindungssysteme, 381) Vierzehn-Elektronen-Elektrocyclisierung des vinylogen Sesquifulvalens - Phenazulen (1981)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 114 (1981), S. 1697-1722 
    Details
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Cyclic Cross-Conjugated Bond Systems, 381) Fourteen Electron Electrocyclisation of the Vinylogous Sesquifulvalene - PhenazuleneThe vinylogous sesquifulvalene 1 thermally undergoes 14-electron electrocyclisation with ease (Ea = 100 ± 2kj·mol-1, log A = 12.0) and perispecifically. Due to the steric constraints imposed by the system it takes place - almost certainly exclusively - in the “symmetry-forbidden”, conrotatory sense to give trans- 10a, 10b-dihydrophenazulene 2a. This is rapidly isomerized into the benzenoid 1,8- and 3,8- dihydrocyclohept[e]indenes 12/15 and is therefore not directly detectable. The trans-stereochemistry in 2a is verified by x-ray crystal analysis of its 1:1-adduct with dimethyl acetylenedicarboxylate (20). The benzylidenecyclohept[e]indenes 28a-c(obtainable from 12/15) could not be isomerised prototropically to the benzylphenazulenes 30a-c. Treatment of the cation 31 (generated from 28a) with nucleophiles also fails to produce phenazulene derivatives (34). The phenazulenium salts 38/39 are, depending on the counteranion, obtainable from 12 (15) in solution (BF-4, ClO-4) or crystalline (SbCl-6, 1/2 PtCl2-6 EE). From the BF-4 salt a deep-blue compound is generated which is stable below -60°C and in the presence of a large excess of DBN, but polymerises above 0°C or in the presence of SiO2 or Al2O3 (-60°C). It is concluded, that this blue species is phenazulene (3).
    Notes: Das vinyloge Sesquifulvalen 1 geht thermisch leicht (Ea = 100 ± 2kJ. Mol-1, log A = 12.0) und perispezifisch die 14-Elektronen-Elektrocyclisierung ein. Unter dem Zwang der Sterischen Verhältnisse erfolgt diese - sehr wahrscheinlich ausschließlich - im “symmetrieverbotenen”, konrotatorischen Sinn zum trans-10a, 10b-Dihydrophenazulen 2a. Dieses ist wegen der raschen Isomerisierung in die benzoiden 1,8- und 3,8-Dihydrocyclohept[e]indene 12/15 direkt nicht nachweisbar. Die trans-Stereochemie in 2a wird durch Röntgenstrukturanalyse seines 1:1-Addukts mit Acetylendicarbonsäure-dimethylester (20) bewiesen. Die aus 12/15 hergestellten Benzyliden-cyclohept[e]indene 28a-c konnten prototrop nicht zu den Benzylphenazulenen 30a - c isomerisiert werden. Phenazulen-Derivate (34) entstehen auch nicht bei der Umsetzung des aus 28a gewonnenen Kations 31 mit Nucleophilen. Die Phenazulenium-Salze 38/39 sind je nach Gegenion in Lösung (BF-4, CIO-4) bzw. kristallisiert aus 12 (15) herstellbar (SbCl-6, 1/2PtCl2-6). Aus dem BF-4-Salz wird eine bei -60°C und großem DBN-Überschuß beständige, tiefblaue Verbindung freigesetzt, die oberhalb 0°C bzw. im Kontakt mit SiO2O3(-60°C) rasch polymerisiert. Es wird argumentiert, daß es sich hierbei um Phenazulen (3) handelt.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/cber.19811140511
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  • 7
    Electronic Resource
    Electronic Resource
    Reaktionen von Carbonylmetall-Anionen mit kationischen Olefinkomplexen: Ethylen-verbrückte Komplexe von Molybdän, Wolfram und Rhenium (1981)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 114 (1981), S. 867-876 
    Details
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Reactions of Carbonyl Metal Anions with Cationic Olefin Complexes: Ethylen Bridged Complexes of Molybdenum, Tungsten, and Rheniumμ 1,2-Ethanediyl-bis(metal) complexes (η5-C5H5)(CO)3MCH2CH2M(CO)3(η5-C5H5) (1a-c),(η5-C5H5) (Ph3P) (CO)2WCH2CH2W(CO)2(PPh3) (η5-C5H5) (3), (η5-C5H5) (CO)3-MCH2 CH2Re(CO)5 (4a-b), and (CO)5ReCH2Re(CO)5 (5) are obtained by nucleophile addition of the carbonylmetallates [M(CO)3(η5-C5H5)] (M = Mo, W) [W(CO)2(PPH3) (η5-C5H5)] and [Re(CO)5] to the coordinated ethylene in the cationic complexes [M(CO)3(η5-C5H5) (η2-C2H4)] + and [W(CO)2(PPh3)η5-C5H5)η2-C2 H4)]+. The structure of 5 was determined by x-ray analysis. The tropylium complexes [M(CO)3(η7-C7H4)] + react with carbonylmetallates to give carbon-carbon coupling with formation of the bi-2,4,6-cycloheptatrien-1-yl compounds (CO)3MC14H14M(CO)3 (M = Cr, Mo, W).
    Notes: Durch nucleophile Addition der Carbonylmetallate [M(CO)3(η5-C5H5)]- (M = Mo, W). [W(CO)2(PPh3)(η5-C5H5)]- und [Re(CO5] an das koordinierte Ethylen in kationischen Komplexen [M(CO)3(η5-C5H5)η2-C2H4] + und [W(CO)2 (PPh3)(η5-C5H5(η2-C2H4)]+ entstehen die μ-1-2-Ethandiyl-bis(metall)-Komplexe (η5-C5H5)(CO)3MCH2CH2M(CO)3(η5-C5H5) (1a-c),(η5-C5H5) (Ph3P) (CO)2WCH2CH2W(CO)2(PPh3) (η5-C5H5) (3) und (η5-C5H5) CO)3 MCH2CH2-Re(CO)5 (4a, b) bzw. (CO)5 ReCH2CH2CH2Re(CO)3(η7-C7H7+ (M = Cr, Mo, W) werden durch Carbonylmetallate unter C—C- Kupplung zu Bi-2,4,6-cycloheptratrien-1-Verbindungen (CO)3MC14H14M(CO)3 reduziert.
    Additional Material: 3 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/cber.19811140305
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  • 8
    Electronic Resource
    Electronic Resource
    Zur Kenntnis der „Säure“ des Roten Roussinschen salzes, (ON)2Fe(SH)2Fe(NO)2 und ihrer Derivate (1981)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 114 (1981), S. 3184-3187 
    Details
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The „Acid“ of Red Roussin's Salt and its derivativesDi-μ-mercapto-tetranitrosyldiiron, (ON)2Fe(SH)2Fe(NO)2 (2), is formed by acidification of an aqueous solution fo Roussin's Red salt, na2[Fe2S2(NO)4], or by reaction of [AsPh4]2[(ON)2Fe(SH)2Fe(NO)]2 (1) with CF3CO2H or HBF4, respectively, and was characterized by analysis and by its infrared and mass spectra. 1 reacts with methyl iodide to give the methylthio-bridged complex (ON)2Fe(SCH3)2Fe(NO2 (3). From 1 and HCI [AsPh4][Fe(NO)2CI2] (65) has been obtained in a nonaqueous solution.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/cber.19811140926
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  • 9
    Electronic Resource
    Electronic Resource
    Diastereoselektive Synthese von β-Nitro- und β-Aminoalkoholen (1981)
    Weinheim : Wiley-Blackwell
    Zeitschrift für die chemische Industrie 93 (1981), S. 422-424 
    Details
    ISSN: 0044-8249
    Keywords: Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Additional Material: 1 Tab.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/ange.19810930433
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  • 10
    Electronic Resource
    Electronic Resource
    Diastereoselective Synthesis of β-Nitro- and β-Aminoalcohols (1981)
    Weinheim : Wiley-Blackwell
    Angewandte Chemie International Edition in English 20 (1981), S. 397-399 
    Details
    ISSN: 0570-0833
    Keywords: Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Additional Material: 1 Tab.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/anie.198103971
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