Phosphorinanon-4-enamine - cycloadditionsreaktionen

Polycyclic carbon-phosphorus heterocycles

“…This anomaly was attributed to the difference in the reactivity of the amine moieties in the elimination step from the dihydro intermediate 219 to give products. 235 These enamines were also found to condense with 1,3-dipoles, such as benzonitrile N-oxide and diphenylnitrile ¡mine (both generated in situ) to give the novel heterocycles 220, 221, and 222.235 Reaction of the pyrrolidine derivative 217 with dimethyl acetylenedicarboxylate afforded the bicyclic 223.235 The reaction of methylphosphonous dichloride and bicyclo[2.2.1 ,]heptadiene (224) at room temperature (24 h) was reported by Green127 to furnish a 1:1 adduct. Hydrolysis of the adduct 225 yielded a crystalline multicyclic phosphine oxide, mp 157 °C.…”

Ringtransformationen heterocyclischer Verbindungen. XII. Neuartige Spiroindoline via Ringtransformation von 2,4,6-Triaryl-pyryliumsalzen mit 2-Methylen-indolinen

“…Abb. 1 SHELXTL-PLUS-Zeichnung [lo] des Spiroindolins 3i; ausgewahlte Bindungsabstande [A] und -winkel ["I: C5-C6 N-C2' 1,482(4); Cl-C6-C5 114,3(3), C2-Cl-C6 110, 9(3), N-1,519(4), Cl-C6 1,571 (5), Cl-C2 1,492(5), C2'-C3' 1,587 (3) [12], Reaktion rnit Methyl(en)ketonen via Enamine [13], Anhydrobasen der Pyridin- [2] und Chinolinreihe [l]): Ahnlich wie dort kann man auch hier davon ausgehen, dalj das Methylenindolin 2 mit dem nucleophilen Enamin-Kohlenstoff in der bevorzugten 2-Position des Pyryliumkations 1 [3,4] unter Bildung der 2H-Pyraninterrnediate 5 [14] [17], l b [18], l c [19], Id, f [20], l e [21] und lg-i [22], des Methylenindolins 2c [23] sowie der Indoliumsalze 2d.HI [24] und 2e.HC104 [25] erfolgte nach Literaturvorschriften. 1,3,3 (3a-e, 3g,h, 3m), EthanollAcetonlChloroform (3f, 3i-I 6-Benzoyl-l',3',3'-trimethyl-3,5-diphenyl-spiro[cyclohexa-2,4-dien-1,2'-indolin] (3a) 65 %, 6-(4-Brom-benzoyl)-3-(4brom-phenyl)-1',3',3'-trirnethyl-5-phenyl-spiro[cyclohexa-2,4-…”