Reaktionen mit Phosphinalkylenen, XIV. Ringschlüsse zu polycyclischen Verbindungen durch Autoxydation von Bis‐triphenylphosphinalkylenen

Abstract

rnDie Autoxydation von Bis-triphenylphosphinalkylenen eraffnet eine neue RingschluDmoglichkeit. Es wird uber die Synthese polycyclischer Verbindungen nach dieser neuen Methode berichtet, bei der die Cyclisierung unter jeweiliger Ausbildung eines neuen 5-, 6-, 7-oder 8-Ringes verlauft.Triphenylphosphinalkylene der allgemeinen Struktur 1 lassen sich mit Sauerstoff in Olefine 2 und Triphenylphosphinoxid (3) iiberfiihren4). Wir berichten im folgenden uber einige nach diesem Schema verlaufende Cyclisierungen, bei denen polycyclische Verbindungen unter Ausbildung eines neuen 5-, 6-, 7-oder 8-Ringes entstehen.In den Formelbildern ist das bei der Autoxydation entstehende Triphenylphosphinoxid fortgelassen. In allen Fallen wurden aus den Dibromiden iiber die Bis-phosphoniumsalze die Bis-Ylide dargestellt. Dieser gesamte Weg ist nur im Beispiel 1.a) aufgefuhrt, wahrend in den anderen Beispielen die Stufen bis zur Bildung des entsprechenden Bis-Ylids fortgelassen sind.

Reactions of phosphorus compounds. XIX. Reactions of 3-(o-formylphenoxy)propyltriphenylphosphonium bromide and 3-(p-formylphenoxy)propyltriphenylphosphonium bromide

“…Found: C, 71.83; H, 5.82. 3-(o-Formylphenoxy)propyltriphenylphosphonium Bromide, 6. -A solution of 243 g (1 mol) of compound 3, 262 g (1 mol) of triphenylphosphine (recrystallized from ether), and 1 1. of dry chlorobenzene was heated at reflux for 3 days under a blanket of dry nitrogen. The product which crystallized on cooling and stirring overnight was washed with six 500-ml portions of chlorobenzene and ten 500-ml portions of anhydrous ether and gave (after drying) 424 g (84%) of salt 6: mp 160-161°; nmr (CDClg) 2.30 (broad, 2), 4.18 (broad t, 2), 4.55 (t, 2), 6.8-S.2 (m, 19, aromatic), 10.30 ppm (s, 1, -CHO).…”

“…Found: C, 82.15; H, 6.88. Reaction of Salt 6 in the Presence of 5-Chlorosalicylaldehyde, 28.-Dry ethanol (200 ml) was distilled into a three-necked flask and allowed to react with 1.58 g (0.0686 mol) of sodium. Phosphonium salt 6 (17.3 g, 0.0343 mol) and 5.4 g (0.0343 mol) of 5-chlorosalicylaldehyde, 28, were added and the solution was refluxed for 4 days with mechanical stirring. The ethanol was removed and the residue extracted with three 100-ml portions of dry ether.…”

Complexes of Alkoxy(dialkylamino)carbenes and Hg2+ Obtained from Dicarbamoylmercury Compounds

“…Reaction of the diimide (1) with methylenebis((dipheny1phosphine) (2) in benzene/acetonitrile (75:lOO v/v) gives the dibromide (3) and heating this at 110-l2O0C in a high vacuum leads to loss of one molar equivalent of methyl bromide with formation of the monobromide (4). A proton can then be removed from the methylene group of (4) by means of liquid ammonia, leading to the uncharged l-methy1-3,3,5,5-tetraphenyl-l-thia-3,5-diphosphav-2,6-diazine (5).…”

“…Reaction of the bisylide ( I ) , readily obtained from 2,2'-bis-(bromomethy1)biphenyl [IJ], with 1 ,Zdicarbonyl compounds (2) in benzene or dioxane gives dibenzonorcaradiene deriva-( 3 ) (5) tives (5), triphenylphosphine oxide (4), and triphenylphosphine (6). We assume that compound (3) is first formed by a Wittig reaction and is then converted into (5) by intramolecular nucleophilic attack by the ylide on the double bondc31 with formation of the cyclopropane ring and loss of triphenylphosphine.…”

Synthesis of hexaoxadiamantanes

“…The preparation of the second and third members of the series, diamantane and triamantane,3 has only recently been published by Schleyer and coworkers,6,6 as has our preliminary account of the synthesis of heteroatom analogs of diamantane. 4 Our approach to the direct chemical synthesis of compounds with a diamantane-type structure made use of the reaction of the hexahydroxycyclohexane isomer scyllitol with appropriate reagents such as orthoformates and phosphites. These reactions proved an interesting challenge since formation of the cage structure required that all six hydroxyls (or their derivatives) be in the energetically unfavorable axial positions.…”