- SYNTHESIS AND REACTIVITY OF P-SUPERMESITYL-C-HALOPHOSPHAALKENES
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The synthesis of the title compounds in high yield via a new route are presented and their reaction with n-butyllithium and subsequent functionalisations is discussed.
- Goede, Simon J.,Schaik, Henk P. van,Bickelhaupt, Friedrich
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- Reaction of Dichlorocarbene with Sterically Protected Phosphabutatriene. Formation of a Stable Dimethylenephosphirane
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The reaction of dichlorocarbene with 4,4-diphenyl-1-(2,4,6-tri-t-butylphenyl)-1-phosphabutatriene gave 2-dichloromethylene-3-diphenylmethylene-1-(2,4,6-tri-t-butylphenyl)-1-phosphirane via 2,2-dichloro-3-(2,2-diphenylethenylidene)-1-(2,4,6-tri-t-butylphenyl)-1-phosphirane. Keywords: dichlorocarbene; phosphabutatriene; phospharadialene; phosphirane; steric protection
- Toyota, Kozo,Yoshimura, Hideki,Uesugi, Takahiko,Yoshifuji, Masaaki
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p. 6879 - 6882
(2007/10/02)
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- Reactions of Dichlorocarbene with Sterically Protected 1-Phosphaallene and 1,3-Diphosphaallene
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Dichlorocarbene reacted with sterically protected 1-phosphaallene and 1,3-diphosphaallene to give a methylene-phosphirane and a methylene-diphosphirane, respectively; the former phosphirane was converted to 1-phosphabutatriene with butyllithium and the st
- Yoshifuji, Masaaki,Toyota, Kozo,Yoshimura, Hideki,Hirotsu, Ken,Okamoto, Akihiro
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p. 124 - 125
(2007/10/02)
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- Synthesis and Reactions of P-Supermesityl-C-halophosphaalkenes
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C-Halophosphaalkenes (1, 2) were prepared in high yield by a one-pot synthesis from HCX3 or CI4 and Mes*PCl2 (Mes* = supermesityl = 2,4,6-tri-tert-butylphenyl).The C-iodophosphoaalkenes Mes*P=Cl2 (1c) and Mes*P=CHI (2c) undergo halogen-metal exchange with n-BuLi at low temperatures.The resulting carbenoids Mes*P=CILi (11c) and Mes*P=CHLi (6) reacted with ClMMe3 (M = Si, Ge, Sn) to give Mes*P=CIMMe3 or Mes*P=CHMMe3 (8-10), respectively.Further reaction of (Z)-13 and (Z)-14 with n-BuLi and ClMMe3 gave Mes*P=C(MMe3)2 (18: M = Ge; 19: M = Sn).The carbenoid (Z)-11c decomposed at -85 deg C; instead of the expected "phosphaisonitrile" Mes*P=C: (21), only Mes*CP (15) was obtained which lends experimental support to the theoretically predicted instability of 21.Key Words: Phosphaalkenes, C-halo, C-metal / "Phospha-isonitrile" / Phosphinylidenemethylene / Phosphaalkyne, E/Z isomers
- Goede, Simon J.,Bickelhaupt, Friedrich
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p. 2677 - 2684
(2007/10/02)
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- Reaction of Dichlorocarbene with Phosphaethylenes. Preparation of Phosphaallene from Phosphaethylene via Dichlorophosphirane
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The reaction of dichlorocarbene with (E)- an (Z)-2-phenyl-(2,4,6-tri-t-butylphenyl)phosphaethylenes gave trans-dichlorophosphirane which was converted to phosphaallene with t-butyllithium, while 2,2-diphenylphosphaethylene gave a vinylphosphaindane derivative.
- Yoshifuji, Masaaki,Yoshimura, Hideki,Toyota, Kozo
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p. 827 - 830
(2007/10/02)
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- Photochemistry of Functionalized Diphosphiranes
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The structure of the functionalized trans-diphosphiranes 1a-e, obtained by reaction of halogenocarbenes with the trans-diphosphene is confirmed by X-ray diffraction.The photolysis of 1a-e lead to the functionalized cis- and trans-1,3-diphosphapropenes 2a-e as major products, via the diphosphiranyl 7 and the diphosphapropenyl 8 radical intermediates.The latter are characterized by ESR spectroscopy using the spin-trap method.The trans configuration of 2a is also confirmed by X-ray diffraction.The mechanism of the ring-opening, involving P-P bond rupture, is discussed.
- Gouygou, Maryse,Tachon, Christine,Koenig, Max,Dubourg, Antoine,Declercq, Jean-Paul,et al.
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p. 5750 - 5756
(2007/10/02)
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- CATIONIC RING OPENING OF FUNCTIONALIZED DIPHOSPHIRANES:
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The functionalized diphosphiranes 1a-c, in presence of Lewis acid, undergo two kinds of reaction:the ring opening leading to the phosphenium-phosphonium ion 2a-c obtained according to an electrocyclic reaction and the fragmentation giving phosphaalkene 3a
- Gouygou, M.,Tachon, C.,Etemad-Moghadam, G.,Koenig, M.
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p. 7411 - 7414
(2007/10/02)
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- NEW ASPECTS OF THE REACTIVITY OF THE FIRST STABLE GERMA- AND STANNAPHOSPHENES
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Various aspects of the reactivity of the first stable germaphosphene 1 and stannaphosphene 6 are described.
- Escudie, J.,Couret, C.,Andrianarison, M.,Raharinirina, A.,Satge, J.
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p. 377 - 380
(2007/10/02)
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- A GENERAL METHOD FOR PREPARING DIPHOSPHIRANES
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Diphosphiranes 3a-3f are obtained by action of diazo derivatives and carbenes on the trans-diphosphene 1.The structures are elucidated by spectroscopic methods.In all cases the cycloaddition reaction is stereoselective.
- Etemad-Moghadam, Guita,Bellan, Jacques,Tachon, Christine,Koenig, Max
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p. 1793 - 1798
(2007/10/02)
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- SYNTHESE UND REAKTIONEN DER 2,4,6-TRI-TERT-BUTYLPHENYLDIHALOGENMETHYLENPHOSPHANE1
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The synthesis of dihalogenated phosphaalkanes 2a,b is reported.After metallation with n-BuLi they could be substituted by halogenated compounds.
- Appel, Rolf,Casser, Carl,Immenkeppel, Michael
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p. 3551 - 3554
(2007/10/02)
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