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  • 1
    ISSN: 0044-2313
    Keywords: Organophosphorus compounds, bicyclic hydrophosphorylation, intramolecular ; methylenebisphosphines ; 1,3-diphosphorinances ; 1,5-diphosphabicyclo[3.3.1]nonanes ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: 1,5-Diphosphabicyclo [3.3.1]nonane1,5-Diphosphabicyclo[3.3.1]nonane 8 has been obtained by free-radical cyclization of CH2=CHCH2(H)PCH2P(H)CH2CH=CH2 6 and 1-allyl-1,3-diphosphorinane 7. For the synthesis of 6 and 7 the chlorophosphine Cl2PCH2PCl2 1 is used as a starting material, which can be converted into Me2N(Cl)PCH2P(Cl)NMe2 3 by reaction with (Me2N)2PCH2P(NMe2)2 2. Treatment of 3 with two equivalents of allyl lithium and cleavage of the PN bonds in CH2=CHCH2(Me2N)PCH2P(NMe2)CH2CH=CH2 4 with diluted HCl affords CH2=CHCH2(H)(O)PCH2P(O)(H)CH2CH=CH2 5. Phenylsilane is used for the first time as a reducing agent to obtain a secundary phosphine like 6 from the secundary phosphine oxide (5). Prolonged heating increases the yield of the byproduct 7 in the mixture of 6 and 7. Reactions of the trivalent phosphorus in 8 with CS2, CH3I, POCl3, NO, sulfur, and KSeCN, respectively, delivers the corresponding derivatives 9-17. The compounds decribed are characterized by 1H, 13C, 31P, 77Se n.m.r., i.r., and m.s. data.
    Notes: 1,5-Diphosphabicyclo[3.3.1]nonan 8 wird durch radikalische Cyclisierung von CH2=CHCH2(H)PCH2P(H)CH2CH=CH2 6 und 1-Allyl-1,3-diphosphorinan 7 erhalten. Ausgangsmaterial für die Synthese von 6 und 7 ist Cl2PCH2PCl2 1, das mit (Me2N)2PCH2P(NMe2)22 quantitativ zu Me2N(Cl)PCH2P(Cl)NMe2 3 reagiert. Die Umsetzung von 3 mit zwei Äquivalenten Allyllithium zu CH2=CHCH2(Me2N)PCH2P(NMe2)CH2CH=CH2 4 und Abspaltung der Me2N-Schutzgruppen mit verdünnter Salzsäure liefert CH2=CHCH2(H)(O)PCH2P(O)(H)CH2CH=CH2 5. Dessen Reduktion zu 6 gelingt mit C6H5SiH3. Daneben entsteht 7, das durch längeres Erhitzen angereichert werden kann. Reaktionen des dreibindigen Phosphors in 8 mit CS2, CH3I, POCl3, NO, Schwefel und KSeCN führen zu den Derivaten 9-17. Die Verbindungen werden durch 1H-, 13C-, 31P- und 77Se-NMR-sowie IR- und MS-Daten charakterisiert.
    Additional Material: 2 Tab.
    Type of Medium: Electronic Resource
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