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BY-NC-ND 3.0 license Open Access Published by De Gruyter June 2, 2014

Das reaktive Verhalten von phenyl-und imidazolylsubstituierten Propenoyldiphenylphosphanen / The Reactive Behaviour of Phenyl and Imidazolyl Substituted Propenoyldiphenylphosphanes

  • Ekkehard Lindner and Efstathios Tamoutsidis

Abstract

The unsaturated acylphosphanes RC(O)PPh2 (4a, b') [R = Ph-CH = CH (a), C3H4N2(Cl)-C(Ph) = CH (b')] are obtained by reaction of RC(O)Cl (3a, b') with (CH3)3SiPPh2. The preparation of 3b' is possible by addition of imidazole to the triple bond of Ph-C=C-C(O)OC2H5 and subsequent hydrolysis of RC(O)OC2H5 (lb) [R = C3H3N2-C(Ph) = CH (b)] and chlorination of RCO2H (2b'). From 4a and imidazole the imidazolide Ph2P(Ph)CH-CH2-C(O)-N2C3H3 (5) is formed which can be oxidized to give Ph2(O)P(Ph)CH-CH2-C(O)-N2C3H3 (6). 4a is coordinated in two different ways to transition metals. A 1:1 molar ratio of 4 a and LnMnTHF [LnMn = (η5-C5H5)Mn(CO)2] yields the P-coordinated complex RC(O)P(Ph2)-MnLn (7a). Excess of LnMn·THF results in the formation of P- and η2-coordinated LnMn-P(Ph2)C(O)(η2-C2H2Ph)MnLn (8a). In the presence of HP(O)Ph2, 4a is oxidized with molecular oxygen to give the phosphorylated alcohol RC[P(O)Ph2]2OH (9a). Via the oxide 10 a and the enol ether Ph2(O)P-CHPh-CH = C(OCH3)P(O)Ph2 (11a) the ester Ph2(O)P-CHPh-CH = C[OC(O)R]P(O)Ph2 (12 a) can be isolated from the Arbusov reaction of 3a and CH3OPPh2.

Received: 1983-1-19
Published Online: 2014-6-2
Published in Print: 1983-6-1

© 1946 – 2014: Verlag der Zeitschrift für Naturforschung

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