Chemie polyfunktioneller Moleküle. 101 [1]: Synthese eines Diphenylphosphin‐substituierten Cyclophosphamide und Röntgenstrukturanalyse seines Oxidations‐produkts

Abstract

Inhaltsübersicht. Diphenylphosphin und rac‐Cyclophosphamid (ClCH2CH2)2NP(O)N(H)(CH2)3O (1) reagieren in Gegenwart von n‐Butyllithium zu einem Zwischenprodukt, das mit Wasser das diphenylphosphinsubstituierte Cyclophosphamid, (Ph2PCH2CH2)2NP(O)N(H)(CH2)3O, (2) bildet. Metallierung von 2 mit n‐BuLi am N(3)‐Atom und Umsetzung mit D2O führt zum N(3)‐Deuteroderivat 2a. Mit H2O2 reagiert 2 zur all‐Phosphinoxid Verbindung, [Ph2P(O)CH2CH2]2NP(O)N(H)(CH2)3O, (4), die mit 0,5 Mol Wasser auskristallisiert und von der zur Charakterisierung des H‐Bückenbindungssystems eine Röntgenstrukturanalyse angefertigt wurde. Die NMR‐Spektren (1H, 13C, 31P, 14N) weisen 2–4 als dynamische Moleküle aus. Chemistry of Polyfunctional Molecules. 101. Synthesis of a Diphenylphosphinesubstituted Cyclophosphamide and the X‐ray Diffraction of its Oxidation Product Diphenylphosphine and rac‐cyclophosphamide, (ClCH2CH2)2NP(O)N(H)(CH2)3O, (1) react in the presence of n‐BuLi to an intermediate which hydrolyses to the diphenylphosphine substituted Cyclophosphamide, (Ph2PCH3CH2)2NP(O)N(H)(CH2)3O, (2). Metallation of 2 with n‐BuLi at the N(3) atom, followed by treatment with D2O yields the N(3)‐deuterated derivative 2a. With H2O2 2 forms the all‐phosphine‐oxide compound, [Ph2P(O)CH2CH2]2NP(O)N(H)(CH2)3O, (4), which crystallizes with 0.5 mole of water. In order to characterize the H‐bridge bonding system a X‐ray structure analysis of 4 was carried out. The NMR‐Spectra (1H, 13C, 31P, 14N) indicate 2–4 as dynamic molecules.

3,5‐Bis(arylidene)piperid‐4‐ones Containing 1,3,2‐Oxazaphosphorinane Moieties: Synthesis and Antitumor Activity

“…The overall geometry of the phosphorus‐containing heterocycle in 4e is also typical for the oxazaphosphorinane compounds with a P‐NC 2 moiety (see, e.g., ), the major difference being the position of the hydrogen atom at N(1)—axial in 4e and equatorial in others. This caused the expected changes in the bond lengths of the heterocycle, in particular relative to 2‐chloro‐2‐oxo‐1,3,2λ 5 ‐oxazaphosphinane 2 , a rather air‐ and moisture‐stable compound, whose structure was also elucidated by X‐ray diffraction (Fig.…”