ADDITION VON DIMETHYLPHOSPHINOXID BZW. -SULFID AN CARBONYLVERBINDUNGEN; DARSTELLUNG VON Ä-Hydroxy-Phosphinoxiden BZW. -SULFIDEN

Catalyst- and Solvent-Free Rapid Addition of Secondary Phosphine Chalcogenides to Aldehydes: Another Click Chemistry

“…6 Hz, СН 2 Р), 29.3 (d, 1 J PC = 37. 9 Hz, СН 2 Р), 29.28, 29.4 (2 d, 2 J CP = 2.5 Hz, PhСН 2 ), 71.5 (d, 1 J CP = 47. 6 Hz, PCH), 122.7 (d, 2 J CP = 3.0 Hz, PCHC=), 126.6 (C m , C 6 H 5 C=), 126.7 (C o , C 6 H 5 C=), 128.3, 128.4 (C o , C 6 H 5 СН 2 ), 128.5 (C p , C 6 H 5 C=), 128.7 (C p , C 6 H 5 CH 2 ), 128.8 (C m , C 6 H 5 CH 2 ), 133.6 (d, 4 J CP = 2.9 Hz, C ipso , C 6 H 5 C=), 133.8 (d, 3 J CP = 11.2 Hz, PhC=), 140.3 (d, 3 J CP = 11.0 Hz, C ipso , C 6 H 5 CH 2 ), 140.5 (d, 3 J CP = 11.8 Hz, C ipso , C 6 H 5 CH 2 ).…”

“…These signals are observed as a doublet at 4.4-6.3 ppm, with the coupling constants 31 Р-С-1 Н of 1.8-11. 9 Hz. Noteworthy, the geminal constants 31 Р-С-1 Н in spectra of some α-hydroxyphosphine chalcogenides are small thus making the splitting of proton resonance signal not always observable.…”

“…Noteworthy, the geminal constants 31 Р-С-1 Н in spectra of some α-hydroxyphosphine chalcogenides are small thus making the splitting of proton resonance signal not always observable. 3,9 As a result, the signals of tertiary phosphine chalcogenides may show up as a singlet. In the 13 С NMR spectra of the compounds 12 and 18, the signals of HОСНР=X fragments appear as a typical doublet at ~63.1-73.5 ppm with the 31 Р-13 С constant being equal to 42.7-87.…”

Darstellung von phosphorylierten Glucosiden durch Umsetzung am Glucosegerüst sowie am Aglycon / Synthesis of Phosphorylated Glucosides through Reaction at the Glucose Framework and at the Aglycon

“…Folgende Ausgangsverbindungen wurden nach Litera turvorschriften synthetisiert: (Hydroxymethyl)-dimethylphosphinoxid 2 [12,13], (Hydroxymethyl)-dimethylphosphinsulfid 5 [14], B enzyl-4,6-0-benzyliden-a-Dglucopyranosid 7 [ 15 -18], 7 -Brompropyl-2,3,4 ,6-tetra-0-benzyl-/3-D-glucopyranosid 9 [ 19], (Tosylmethyl)-dimethylphosphinoxid 3: Ein Gemisch aus 11.58 g (148 mmol) Dimethylphosphinoxid und 4.45 g (148 mmol) Paraformaldehyd wurde nach langsamer Temperaturerhöhung (exotherme Reaktion) 2 h bei 140°C unter Rückfluß erhitzt. Nach Zugabe von 50 ml Toluol wurde die organische Phase zweimal mit je 20 ml dest.…”

Reaction of secondary phosphine oxides with acylacetylenes

“…Of particular interest are polyfunctionalized tertiary phosphine oxides; however, their synthesis involves some difficulties. A convenient synthetic approach to such compounds is based on the addition of secondary phosphine oxides to functionally substituted alkenes [15][16][17][18], alkynes [15,17] (including α,β-acetylenic ketones [19]), aldehydes [20][21][22][23][24], and ketones [20,21]. In the recent publication [25] we briefly reported on reactions of secondary phosphine oxides with 1-acetyl-and 1-butanoyl-2-phenylacetylenes in the system KOH-THF, which occurred in chemoselective fashion at the C=O group and led to the formation of functionalized tertiary phosphine oxides having a hydroxy group and an acetylenic fragment.…”