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  • Fluorophosphates  (1)
  • Halomethylphosphonium Halides  (1)
  • Organylfluorophosphanes  (1)
  • 1
    ISSN: 0044-2313
    Keywords: Halomethylphosphonium Halides ; Bisphosphonium Salts ; Phosphoranylphosphonium Salts ; Transalkylation ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: On the Reaction of Halomethylphosphonium Halides, [R3PCYnX3-n]X, with Phosphanes, R′3PThe results of the reaction of 19 different halomethylphosphonium halides, [R3PCYnX3-n]X (R = Ph, n-Bu, Me2N, Et2N; Y = H, F; X = Cl, Br, I; n = 0-2), with Ph3P, n-Bu3P, and (R2N)3P are presented. As reaction products bisphosphonium salts, [R3P—CYnX2-n—PR′3]X2, and phosphoranylphosphonium salts, [R3P=CY—PR′3]X, or reduced (halo)methyl-phosphonium salts, [R3PCHYnX2-n]X, are obtained. [Ph3PCBrF2]Br and [Bu3PCBrF2]Br react with R′3P by trans-alkylation forming [R′3PCBrF2]Br. The factors influencing the course of the reaction are discussed.
    Notes: Es wird über die Reaktion von 19 verschiedenen Halomethylphosphoniumsalzen, [R3PCYnX3-n]X (R = Ph, n-Bu, Me2N, Et2N; Y = H, F; X = Cl, Br, I; n = 0-2), mit Ph3P, n-Bu3P und (R2N)3P berichtet. Als Reaktionsprodukte werden Bisphosphoniumsalze, [R3P—CYnX2-n—PR′3]X2, und Phosphoranylphosphoniumsalze, [R3P=CY—PR′3]X, oder reduzierte (Halo)methylphosphoniumsalze, [R3PCHYnX2-n]X, erhalten. [Ph3PCBrF2]Br und [Bu3PCBrF2]Br reagieren mit R′3P unter Umalkylierung zu [R′3PCBrF2]Br. Die den Reaktionsverlauf beeinflussenden Faktoren werden diskutiert.
    Additional Material: 5 Tab.
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  • 2
    ISSN: 0044-2313
    Keywords: Organylfluorophosphanes ; reaction mechanism ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: The Dimerization of Di(n-butyl)fluorophosphane and its Reaction with BenzaldehydeThe phosphorus atom of organylfluorophosphanes possesses electrophilic as well as nucleophilic properties. This dualistic character decisively determines both their disproportionation and their reaction with aldehydes. The phoshanylphoshorane n-Bu2P—PF2(n-Bu)2, 1 b, has been proved to be the intermediat product of the disproportionation of n-Bu2PF. In the presence of an equimolar amount of Et3N an equilibrium exists between 1 b and the monomeric n-Bu2PF. n-Bu2PF react with benzaldehyde forming the phosphinitophoshorane n-Bu2P′—O—CHPh—PF2(n-Bu)2, 3 a. Reliable information on the reaction pathway has been obtained by means of crossing experiments.
    Notes: In Organylfluorphosphanen besitzt das Phosphoratom sowohl elektrophile als auch nucleophile Eigenschaften. Dieser dualistische Charakter ist für die Disproportionierung von Diorganylfluorphosphanen, R2PF, und für ihre Reaktion mit Aldehyden von entscheidender Bedeutung. Bei der Disproportionierung von n-Bu2PF tritt das Phosphanylphosphoran n-Bu2P—PF2(n-Bu)2, 1b, als Zwischenprodukt auf. In Gegenwart von äquimolaren Mengen Et3N steht 1 b mit dem monomeren n-Bu2PF im Gleichgewicht. n-Bu2PF reagiert mit Benzaldehyd zum Phosphinitophosphoran n-Bu2P′—O—CHPh—PF2(n-Bu)2, 3 a, dessen Bildungsweg durch „Kreuzungsexperimente“ eindeutig ermittelt werden konnte.
    Additional Material: 1 Ill.
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  • 3
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Zeitschrift für anorganische Chemie 621 (1995), S. 865-870 
    ISSN: 0044-2313
    Keywords: Fluoridolysis ; N-Phosphoryl Phosphazenes ; Fluorophosphates ; Diazadiphosphetine ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Fluoridolysis of N-Phosphoryl PhosphazenesIn the reaction of the N-phosphoryl phosphazenes X3P=N—P(Y)X2 (X = Cl, PhO, Et2N, CF3CH2O, PrS, Ph; Y = O, S) (1-18) with Et3N · nHF (n ≍ 3 or 0.6) fluoro derivatives of N-phosphoryl phosphazenes (see table 2) as well as N-phosphorylated imiddotetrafluorophosphates, [F4P=N—P(Y)Cl2]- (Y = O, S), and imidopentafluorophosphates, [F5P—N—P(Y)X2]2- or [F5P—NH—P(O)X2]- (see table 3), are formed. t-BuNHPCl2=N—POCl2 reacts in acetonitrile with Et3N or i-Pr2EtN to form a product, representing probably the diazadiphosphetine (5 b).
    Notes: Bei der Umsetzung der N-Phosphorylphosphazene X3P=N—P(Y)X2 (X = Cl, PhO, Et2N, CF3CH2O, PrS, Ph; Y = O, S) (1-18) mit Et3N · nHF (n ≍ 3 oder 0,6) werden durch den Austausch von Chlor sowie PhO-, Et2N- und CF3CH2O-Gruppen gegen Fluor Fluorderivate von N-Phosphorylphosphazenen (siehe Tab. 2) sowie N-phosphorylierte Imiddotetra- und -pentafluorophosphate, [F4P=N—P(Y)Cl2]- (Y = O, S) und [F5P—N—P(Y)X2]2- bzw. [F5P—NH—P(O)X2]- (siehe Tab. 3) gebildet. t-BuNHPCl2=N—POCl2 reagiert in Acetonitril mit Et3N oder i-Pr2EtN zu einem Produkt, bei dem es sich höchstwahrscheinlich um das Diazadiphosphetin (5 b) handelt.
    Additional Material: 5 Tab.
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