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  • 1
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 106 (1973), S. 3461-3462 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Type of Medium: Electronic Resource
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  • 2
    ISSN: 0030-493X
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: It is shown by deuterium-labelling experiments, that a substantial part of the [M - CH2OH]+-ions from 2-methyl-2-phenyl-propane-1,3-diol must have rearranged to carbonyl-oxygen protonated phenylacetone by a positional interchange of the phenyl- and hydroxyl groups prior to decomposition.
    Additional Material: 1 Ill.
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  • 3
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    Helvetica Chimica Acta 56 (1973), S. 440-449 
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: 4-Vinylpyridine (1a) combines with 3 moles of dienophilic N-alkyl-maleinimides (2) in the presence of polymerization inhibitors. The first step of the reaction probably consists of 1:1-addition with participation of an aromatic double bond, comparable to the analogous behavior of styrene and its derivatives under similar conditions. The unstable intermediates 3, like other Schiff bases (imines), add 2 further moles of the N-alkyl-maleinimides forming the spiro compounds 4. These are split in an acidic medium into the N-alkyl-5,6,7,8-tetrahydroisoquinoline-7,8-dicarboximides (5), and N,N′-dialkyl-2-butene-1,2,3,4-tetracarboxylic 1,2,:3,4-diimides (6). LiAlH4 reduction of these two types of compounds leads to N-alkyl-1 H-(3,4-d)-pyrrolo-2,3,3a,4,5,9b-hexahydroisoquinolines (7) and to N,N′dialkyl-3,3′-bipyrrolidyls (8A) and their dehydro-products 8B, respectively.From the reaction of 2-vinylpyridine (1b) with N-alkyl-maleinimides (2) the 1:2-addition products 9 can be isolated in the presence of polymerization inhibitors, which are derivatives of N-alkyl-5,6,7,8-tetrahydroquinoline-5,6-dicarboximides (9). This again corresponds to the reaction type of cycloadditions with styrene. Furthermore 1:3 adducts are formed which according to 1H- and 13C-NMR.-data most likely have the structure 10, representing a new type of cycloaddition involving the pyridine nitrogen.
    Additional Material: 3 Tab.
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  • 4
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    Helvetica Chimica Acta 56 (1973), S. 519-524 
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The synthesis of a new (-)-Δ8-6a,10a-trans-tetrahydrocannabinol analogue, containing a N-methyl-3-propyl-pyrrolidin-3-yl side-chain, is reported.
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  • 5
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    Helvetica Chimica Acta 56 (1973), S. 1406-1413 
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: N-Methylimidazole (N-M), in boiling acetonitrile, catalyzes the oligomerization of N-alkyl maleimides (2) to tri-, tetra-, penta- and hexamers. In the presence of small amounts of hydroquinone the trimers of 2 are formed, which have the structure of N,N′,N″-trialkyl-cyclohexane-1,2,3,4,5,6-hexacarboxy-1,2:3,4:5,6-tri-midies (6). A possible mechanism of this catalytic cyclo-oligometization is discussed. Dependant from the chemical nature of the N-alkyl substituent of the maleimides, imidazole or benzimidazole and some of its C-substituted products also can function as oligomerization catalysts. However in this case the normal 1:1 addition is the main reaction, as observed also with pyrazoles plus 2. Maleic dimethylester was isomerized to fumaric dimethylester in the presence of N-methylimidazol. These observations reveal additional catalytic functions to the well known hydrolysis catalyzing properties of imidazoles.
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  • 6
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Biopolymers 12 (1973), S. 373-385 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The existence of a soluble complex formed by polyuridylic acid (poly (U)) and 3′,5′-cyclic AMP (cAMP) is demonstrated by u.v. extinction vs. temperature curves, optical rotation, equilibrium dialysis, and reaction calorimetry. The complex hasthe stoichiometry of 2 poly (U)-cAMP and its formation is accompanied by an enthalpy change of -13.0 kcal/mole of base triplet. The introuction of an empirical factor α in the equations given by Damle2 and Crothers2 leads to the evolution of a ΔH value of -13.4 keal/mole. The parameter α is considered as a correction factor for the concentration dependence of the binding process. There is no relation between α and the reduction of monomer activity due to self-association of monomers. The study of the binding process at several temperatures showed that the cooperativity parameter, σ, is independent of temperature and its value of 6.5 × 10-3 is in good agreement with σ = 5 × 10-3 for the poly (U)·poly(A) system.3
    Additional Material: 8 Ill.
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  • 7
    ISSN: 0044-2313
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Spinels with substituted Nonmetal Sublattices. IV. CuCr2(S1-xSex)4 and CuCr2(Se1-xTex)4Polycrystalline samples of the spinel system CuCr2(S1-xSex)4 have been prepared with 0 ≤ x ≤ 1. We found that in the spinel system CuCr2(Se1-xTex)4 no solid solution is existent in the range 0.01 ≤ x ≤ 0.70. When S is substituted by Se and Se by Te the lattice constants increase linearely by 0.52 Å and 0.81 Å respectively. The anion-sublattice shows random distribution of the chalcogen atoms, the chalcogen parameters u are constant in the system CuCr2(S1-xSex)4 with a mean value of u = 0.3829. The calculated anion-cation-distances lead to a covalent tetrahedral radius rCu = 1.23 Å. This radius is in agreement with the radius rCu = 1.22 Å of Cu spinels with Cu in the valence +1.
    Notes: Im Spinellsystem CuCr2(S1-xSex)4 erfolgt im Bereich 0 ≤ x ≤ 1 lückenlose Mischkristallbildung, während beim Spinellsystem CuCr2(Se1-xTex)4 in diesem Bereich zwischen 0,01 ≤ x ≤ 0,70 eine Mischungslücke auftritt. Beim Ersatz von S durch Se wächst die Gitterkonstante a linear um 0,52 Å, beim Ersatz von Se durch Te linear um 0,81 Å. Das Anionenteilgitter ist statistisch mit Chalkogenatomen besetzt. Die Chalkogenparameter im System CuCr2(S1-xSex)4 sind konstant, der Mittelwert beträgt u = 0,3829. Aus den berechneten Anionen-Kationen-Abständen erhält man einen kovalenten Tetraederradius rCu = 1,23 Å. Dieser Radius stimmt mit dem Radius rCu = 1,22 Å überein, den man aus Cu-Spinellen mit Cu in der Oxydationsstufe +1 erhält.
    Additional Material: 1 Ill.
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  • 8
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Zeitschrift für anorganische Chemie 397 (1973), S. 31-39 
    ISSN: 0044-2313
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Hexakis(trifluorophosphine) Complexes of Chromium(0), Molybdenum(0), and Tungsten(0)The reaction of tris(π-allyl)chromium with PF3 at low pressure yields deep darkgreen tris(π-allyl)-trifluorophosphine chromium which is slowly converted into hexakis(trifluorophosphine) chromium: If tris(π-allyl)chromium is reacted with PF3 at high pressure, the only isolable product is Cr(PF3)6. Anhydrous molybdenum(V) and tungsten(VI) chloride react with PF3 in the presence of copper to the hexakis(trifluorophosphine) complexes of the zerovalent metals: The hexakis(trifluorophosphine) complexes are thermally very stable, crystalline, colourless solids.
    Notes: Eine ätherische Lösung von Tris(π-allyl)-chrom setzt sich unter geringem Trifluorphosphindruck zu tief dunkelgrünem Tris(π-allyl)-trifluorphosphinchrom um, das langsam zu kristallinem, farblosen Hexakis(trifluorphosphin)-chrom(0) weiterreagiert: Bei den Hochdruckumsetzungen des kristallinen Tris(π-allyl)-chrom konnte nur das Endprodukt Cr(PF3)6 isoliert werden. Wasserfreies Molybdän(V)-chlorid und Wolfram(VI)-chlorid bilden in Gegenwart von Kupfer als halogenbindendem Beimetall unter Trifluorphosphindruck die ebenfalls kristallinen, farblosen Hexakis(trifluorphosphin)-metall(0)-Komplexe: .
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  • 9
    ISSN: 0044-2313
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Fluorine Exchange in Trifltiorophosphinemetal Complexes. IVThe Reaction of Nitrosyltrifluorophosphirie Complexes of Iron and Cobalt with Alkoxid- and Hydroxid-IonsFe(NO)2(PF3)2, 1, and Co(NO)(PF3)3, 2, react with alcoxids and phenoxid by a complete F/OR-exchange to the corresponding phosphite complexes Fe(NO)2P(OR)3)2 and Co(NO)(P(OR)3)3, (R = CH3, C2H5, n-C3H7, i-C3H7, n-C4H9, C6H5), 3-13. The nitrosyltrifluorophosphine complexes 1 and 2 change only one or two fluorine atoms against OH--ions to give difluorophosphito complexes: The reaction of 1 with a diisopropylamine/water mixture yields the bis(difluorophosphito) complex [Fe(NO)2(PF2O)2]2-, 15, with 2 under identical conditions [Co(NO)(PF3)2 PF2O]-, 14, is obtained; 1 and 2 react with Ba(OH)2 in THF to give [Fe(NO)2(PF3)PF2O]- resp. 14, the latter reacts under harder conditions partially to [Co(NO)(PF3)(PF2O)2]2-. These difluorophosphito complexes, which are isolated as salts with the cations [(i-C3H7)2NH2]+ and Ba2+, can be alkylated to the corresponding difluorethoxyphosphine derivates of 1 and 2, Fe(NO)2 (PF3)2-n(PF2OC2H5)n (n = 1,2) and Co(NO)(PF3)2PF2OC2H5. All compounds are characterised by IR and mass spectra.
    Notes: Fe(NO)2(PF3)2, 1, und Co(NO)(PF3)3, 2, tauschen bei der Umsetzung mit Alkoholaten und Phenolat sämtliche Fluoratome gegen RO-Gruppen aus unter Bildung der entsprechenden Phosphitkomplexe Fe(NO)2(P(OR)3)2 bzw. Co(NO)(P(OR)3)3 (R = CH3, C2H5, n-C3H7, i-C3H7, n-C4H9, C6H5), 3-13. Beide Nitrosyl-trifluorphosphin-Komplexe gehen maximal nur einen zweifachen F/OH-Austausch zu Difluorphosphito-Komplexen ein: In einem Diisopropylamin/Wasser-Gemisch liefert 1 den Bis(difluorphosphito)-Komplex[Fe(NO)2(PF2O)2] 2-, 15, 2 unter gleichen Bedingungen [Co(NO)(PF3)2PF2O- 14; die Umsetzung von 1 und 2 mit Ba(OH)2 in Tetrahydrofuran führt zu [Fe(NO)2(PF3) PF2O]- bzw. 14, welches sich unter drastischen Bedingungen teilweise zu [Co(NO)(PF3) (PF2O)2]2- umsetzt. Diese Difluorphosphito-Komplexe, die als Salze mit den Kationen [(i-C3H7)2NH2]+ bzw. Ba2+ anfallen, können zu den entsprechenden Difluoräthoxy-Derivaten von 1 und 2, Fe(NO)2 (PF3)2-n(PF2OC2H5)n (n = 1, 2) bzw. Co(NO)(PF3)2PF2OC2H5, alkyliert werden. Sämtliche Verbindungen werden anhand der IR- und Massenspektren charakterisiert.
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  • 10
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Zeitschrift für anorganische Chemie 396 (1973), S. 1-6 
    ISSN: 0044-2313
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Contributions to the Chemistry of Hydrazine and its Derivatives. XXXVI. On the Pernitrides and Nitrogen Complexes of Barium, Strontium, and CalciumFor further characterization of the alkaline earth pernitrides M3N4 (M = Ba, Sr, Ca) as well as the alkaline earth-nitrogen complexes, which can be obtained from them, magnetical studies were carried out. Whereas barium and calcium pernitride show paramagnetism and strontium pernitride weak diamagnetism, the nitrogen complexes are diamagnetic. The barium-nitrogen complex was treated with carbon monoxide under high pressures at different temperatures. Although no exact ligand exchange occurred, a partial addition of the CO molecule was noticed. By reaction of barium pernitride with carbon monoxide at 250°C and 450 at barium cyanide was produced in high yield.
    Notes: Zur weiteren Charakterisierung der Erdalkalimetallpernitride Me3N4 (Me = Ba, Sr, Ca) sowie der daraus darstellbaren Erdalkalimetall-Stickstoff-Komplexe wurden magnetische Untersuchungen durchgeführt. Während Barium- sowie Calciumpernitrid Paramagnetismus und Strontiumpernitrid schwachen Diamagnetismus aufwiesen, sind die Stickstoff-Komplexe diamagnetisch. Der Barium-Stickstoff-Komplex wurde unter hohen Drücken bei verschiedenen Temperaturen mit Kohlenmonoxid umgesetzt, wobei zwar kein echter Ligandenaustausch, wohl aber eine teilweise Addition der CO-Molekel beobachtet werden konnte. Die Behandlung von Bariumpernitrid mit Kohlenmonoxid bei etwa 250°C und 450 at liefert in hoher Ausbeute Bariumcyanid.
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