Inhaltsu È bersicht. 1-Phosphabicyclo[3.2.1]octan erha Èlt man durch radikalische Ringschluûreaktion von (2-Vinyl-4-pentenyl)-phosphan in Gegenwart von AIBN. Ein weiterer Weg zu 1-Phosphabicyclo[3.2.1]octanen beruht auf der radikalischen Cyclisierung von 2-Methyl-4-allyl-phospholan, das bei der Reaktion von (2-Allyl-4-pentenyl)-phosphan mit KPH 2 /18-Krone-6 in THF entsteht. Die bicyclischen Phosphane werden durch Reaktionen mit CS 2 , Selen, Schwefel, NO, CH 3 I und HSO 3 F, Struktur-und analytische Daten sowie 1 H-, 13 C-, 31 P-und 77 Se-NMR-Spektren charakterisiert. Der Raumbedarf der Phosphane als Komplexliganden wird entsprechend dem Tolman-Modell aus den 31 P± 1 H-Kopplungskonstanten abgescha È tzt. Die Konfiguration der Methylsubstituenten sowie die Konformation des Sechsringes wird aus den NMR-Parametern (Kopplungskonstanten, NOE's) bestimmt und durch die Ro È ntgenkristallstrukturanalyse besta È tigt. 1-Phosphabicyclo[3.2.1]octanesAbstract. 1-Phosphabicyclo[3.2.1]octane has been obtained by free-radical cyclization of (2-vinyl-4-pentenyl)-phosphane in the presence of AIBN. Another approach to 1-phosphabicyclo[3.2.1]octanes involves free-radical cyclization of 2-methyl-4-(2-propenyl)-phospholane synthesized by the reaction of [2-(2-propenyl)-4-pentenyl]-phosphane with KPH 2 / [18]crown-6 in THF. The bicyclic phosphanes are characterized by reactions with CS 2 , selenium, sulfur, NO, CH 3 I, and HSO 3 F, respectively, structural and analytical data as well as 1 H, 13 C, 31 P, 77 Se NMR spectral measurements. The steric crowding of the phosphanes as complex ligands has been estimated from 31 P± 1 H coupling constants according to the Tolman model. The configuration of the methyl substituents as well as the conformation of the six-membered ring were determined by NMR parameters (coupling constants, noe's) and proved by X-ray crystal structure analysis.
A new approach to 1‐phosphabicyclo[3.3.0]octane compounds starts from the reaction of 4‐chloro‐hepta‐1.6‐diene with Mg in THF. No Grignard rearrangement is observed. The Grignard reagent is converted into 1‐allyl‐3‐butenylphosphonous dichloride followed by reduction with LiAlH4. Cis‐1‐phosphabicyclo[3.3.0]octane has been prepared by radical‐initiated cyclization of 1‐allyl‐3‐butenylphosphane. The bicyclic phosphane is characterized by analytical data as well as 31P and 13C NMR measurements and the reactionswith NO, S8, KSeCN, CH3I, Ni(CO)4 and HSO3F, respectively.
Inhaltsübersicht. exo-endo-und exo-exo-2,6-Dimethyl-1-phosphabicyclo[2.2.1]heptan wurden durch Ringschlußreaktion von 2-Methyl-4-allyl-phospholan in Gegenwart der komplexen Base Natriumsalz des Diethylenglycolmonoethylethers / Natriumamid in THF (NAMEDEG) erhalten. Die Charakterisierung der bicyclischen Phosphane erfolgte durch Derivatisierungsreaktionen mit Selen, Schwefel, (CH 3 ) 2 SeO, CH 3 I und HSO 3 F und Charakterisierung der Reaktionsprodukte durch Elementaranalyse, Röntgenstrukturana-lyse sowie 1 H-, 13 C-und 31 P-NMR-Spektren. Der Raumbedarf der 1-Phosphabicyclo[2.2.1]heptanesAbstract. Exo-endo-and exo-exo-2.6-dimethyl-1-phosphabicyclo [2.2.1]heptane have been obtained by cyclization of 2-methyl-4-(2-propenyl)phospholane in the presence of the complex base, sodium salt of diethylenglycolmonoethylether -sodium amide in THF (NAMEDEG). The bicyclic phosphanes are characterized by reactions with selenium, sulfur, (CH 3 ) 2 SeO, CH 3 I, and HSO 3 F, respectively, elemental analysis, X-ray crystal structure analysis as well as 1 H, 13 C, 31 P NMR spectral measurements. The steric demand of these phosphanes as complex ligands has been estimated from the Einleitung
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