Reactions of tervalent phosphorus–nitrogen compounds. Part I. Polyhalogenated alkanes

Abstract

Aminophosphines of the general structure R,P*NHR' (R = Ph or OEt; R' = Ph or Pr") react rapidly with carbon tetrachloride and bromotrichloromethane to give phosphinimines R,P(X): NR' (X = Br, or CI) and chloroform. The reaction proceeds by initial reaction on positive halogen followed by deprotonation of the phosphonium salt. In addition to chloroform, low yields of carbon tetrachloride and bromodichloromethane were detected in the reaction with bromotrichloromothane, showing that the trichlorornethyl carbanion is formed in the free state.PHOSPI~INES are known to react readily with polyhalogen compounds, usually by nucleophilic displacement on positive halogen, whereas the corresponding reactions of trialkyl phosphites are generally regarded as freeradical pr0cesses.l Thus, triphenylphosphine reacts with carbon tetrachloride a t normal temperatures,2 and exothermically with the t e t r a b r ~m i d e . ~ These reactions were considered to lead to the corresponding dihalogenomethylenephosplioranes, which were not isolated but converted directly into the dihalogeno-2Ph,P + CX, Ph3PX, + Ph,P:CX, (X = CI or Br)

ChemInform Abstract: Synthesis of the 6‐C‐Methyl and 6‐C‐(Hydroxymethyl) Analogues of N‐Acetylneuraminic Acid and of N‐Acetyl‐2,3‐didehydro‐2‐deoxyneuraminic Acid.

“…In these cases, the relative chemical shift values of the two H-C(3) are not altered, H,-C(3) always being observed at higher field than HB-C(3). The anomeric configuration of 44 and 45 is again in agreement with Hudson's rule [29], irrespective of the conformational differences.…”

“…A 'C,-confomation appears to be compatible with the former 1,3 interaction, while the latter one forces the pyranose ring into a boat conformation. In spite of the different conformations of the anomers, Hudson's rule [29] is followed. Treatment of 27 or 28 with 0 .…”

Homoleptic Lanthanide Complexes of Chelating Phosphanamides—An Experimental and Theoretical Study

“…The new complexes have been characterized by standard analytical and spectroscopic techniques, and the solid-state structures of 2 b and 2 c (Figure 1) as well as of the neutral ligand Ph 2 PN(H)Ph (3) [5] were established by single-crystal X-ray diffraction. [6] Crystals of 2 b and 2 c that consist of an ion pair composed of a [Li(thf) 4 ] cation and a [(Ph 2 PNPh) 4 Ln] À anion are isomorphous.…”

Orthometalation of Functionalized Phosphinoamines with Late Transition Metal Complexes

“…The new ligands o -Ph 2 PN(H)C 6 H 4 X [X = C(O)CH 3 , 1 ; X = C(O)Ph, 2 ], closely related to Ph 2 PN(H)C 6 H 5 , were successfully synthesized from cheap, commercially available Ph 2 PCl and o -H 2 NC 6 H 4 X in respectable yields (ca. 70%).…”