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  • 1
    ISSN: 0044-2313
    Keywords: N-dichlorophosphanyl triphenylphosphazane ; N-phosphanyl, N-phosphinoyl phosphazenes ; 31P n.m.r. data ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Replacement and Oxidation Reactions of N-Dichlorophosphanyl Triphenylphosphazene, Ph3P=N—PCl2The title compound (1) reacts with MeOH, EtOH, PhOH, EtSH, and water forming N-phosphanyl or N-phosphinoyl phosphazenes, resp., Ph3P=N—PX2 (X = OPh(8), SEt(9)) or Ph3P=N—PH(O)X (X = Cl(3), OH(4), OMe(5), OEt(7)). The reaction of 1 with P(NEt2)3 yields Ph3P=N—P(NEt2)2 (10). Ph3P=N—PF2(11) and Ph3P=N—PH(O)F (12) are obtained by chlorine-fluorine exchange. The N-phosphanyl compounds 1, 8, 9 and 11 are oxidized by NO2 yielding the corresponding N-phosphoryl derivatives, Ph3P=N—P(O)X2 (X = Cl(2), OPh(13), SEt (14), F(15)). The thiophosphoryl compounds, (Ph3P=N—P(S)X2 (X = Cl(16), OPh(17), F(18)) are obtained by oxidizing 1, 8, and 11 with sulfur.
    Notes: Die Titelverbindung (1) reagiert mit den protischen Nucleophilen MeOH, EtOH, PhOH, EtSH und Wasser zu Phosphanyl- bzw. Phosphinoylphosphazenen, Ph3P=N—PX2 (X = OPh (8), SEt (9)) bzw. Ph3P=N—PH(O)X (X = Cl(3), OH(4), OMe(5), OEt(7)). Die Reaktion von 1 mit P(NEt2)3 ergibt Ph3P=N—P(NEt2)2 (10) und durch Chlor-Fluor-Austausch werden Ph3P=N—PF2 (11) und Ph3P=N—PH(O)F (12) erhalten. Die N-Phosphanylverbindungen 1, 8, 9 und 11 werden durch NO2 zu den entsprechenden N-Phosphorylderivaten Ph3P=N—P(O)X2 (X = Cl(2), OPh(13), SEt (14), F(15)) und die Verbindungen 1, 8 und 11 durch Schwefel zu Thiophosphorylverbindungen (Ph3P=N—P(S)X2(X = Cl(16), OPh(17), F(18)) oxydiert.
    Additional Material: 1 Tab.
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  • 2
    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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