Organonickel(II)‐Komplexe des Typs [NiX{C6H3(CH2NR1R2)2‐2,6}] (X = Halogen, OH2+/CF3SO3−; R1R2Et 1; R1R2iPr 2; R1 = Me, R2 = Cy 3; (NR1R2) = piperidino 4; (NR1R2) = pyrrolidino 5) werden beschrieben. Die Charakterisierung erfolgte mit Hilfe der 1H und 13C‐NMR‐ sowie der UV/Vis‐Spektroskopie. Von 1 a (X = Br) wurde die Kristallstruktur bestimmt. Dieser Komplex kristallisiert orthorhombisch in der Raumgruppe Pbca mit a = 1 335,8(2) pm, b = 1 903,3(3) pm, c = 1 365,4(3) pm und Z = 8, er besitzt eine annähernd quadratisch‐planare Geometrie. 4 und 5 vermögen SO2 reversibel zu fixieren, was durch die IR‐Photoakustik‐Spektroskopie nachweisbar ist. Die Reaktionen von 1–5 mit CS2 und PhNSO werden diskutiert.
N,N‐Dialkylamides of 2‐Hydroxy‐2‐phenyl‐cyclopropan‐1‐carboxylic Acid – Photochemical Synthesis and Determination of the Structure
Irradiation of N,N‐dialkylamides of β‐benzoylpropionic acid 2a, b in ether by n,π*‐excitation leads to the corresponding amides of the hitherto unknown 2‐hydroxy‐2‐phenyl‐cyclo‐propancarboxylic acid 3a, b, 4a, b. The photocyclization yields diastereomeric mixtures E:Z = 2.5–3:1. The determination of the relative configurations is based on the different tendency of dimerization of the E and Z diastereomers.
Synthesis of trans‐4‐Diphenylphosphinyl Stilbenes
The reaction of 4‐tolyl‐diphenylphosphine oxide with N‐bromosuccinimide results in 4‐diphenylphosphinyl benzylbromide 5 which can be easily converted to (4‐diphenylphosphinyl)‐benzyl triphenylphosphonium bromide 6 and (4‐diphenylphosphinyl)‐benzyl diphenylphosphine oxide 7, respectively. In the presence of strong bases 6 and 7 react with aromatic aldehydes 8 to the 4‐diphenylphosphinyl substituted stilbenes 1. The yields depend on the nature of base and solvent. The trans configuration of 1 is determined by i.r. and 1H‐n.m.r. measurements.
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