C3S 32⊖, hinter dieser Summenformel verbirgt sich das kleinstmögliche Thioxokohlenstoff‐Dianion, das jetzt in Form mehrerer Salze, z. B. 1, erhalten werden konnte. Aus der Röntgenstrukturanalyse von 1 lassen sich wertvolle Informationen über das Bindungssystem dieses Dianions mit ideal delokalisierten π‐Elektronen gewinnen.
Suitably "push-pull"-substituted carbonyl ylides",'' or thiocarbonyl y l i d e~~~] have sufficient stability for isolation and have been the subject of several detailed investigations during the last ten years. Isolable selenocarbonyl ylides, on the other hand, were hitherto unknown.l4I We report here on the synthesis and characteristic properties of the first stable compounds of this type with cyclopropenylium and bis(methy1ene) or bis(imino)cyclopropanide functions as stabilizing termini.As we have found, the selone function in the diaminocyclopropeneselones 1, which are readily accessible from the cyclopropenylium salts 6 and sodium hydrogen selenide,15] is sufficiently nucleophilic to displace triethylamine from the zwitterions 216] or 3."] For the synthesis of 4a [yield 84%, m.p. 178°C (dec.)], one hours' heating in anhydrous dichloromethane until complete removal of triethylamine suffices; the synthesis of 5c (yield 85%, m.p. 230°C (dec.) was achieved by one hours' reaction in boiling ethanol. On cooling the reaction solution the desired selenocarbonyl ylides 4 and 5 precipitate as colorless to pale-beige, airstable crystals and can be recrystallized from nitromethane. 4c [m.p. 207°C (dec.)] could be obtained in 52% yield via another route. 2 was converted with freshly prepared sodium hydrogen selenide into the salt 7,"' which reacts smoothly with the salt 6cl9I to yield the selenocarbonyl ylide 4c.
Neue Dianion-sulfide l a -c entstehen bei der Reaktion der Kaliumsalze von Thiodeltaten 4a,b mit den Deltainen 5a,b. Die Darstellung neuer Thiocarbonyl-ylide 7a-d bzw. 8a-d mit Cyclopropenium-und Deltatfunktionen gelingt durch Umsetzung der Thione 6a -d mit den Deltainen 5a, b oder aus dem Cyclopropenium-Salz 9 mit dem Kalium-thiodeltat 4a. Interessanterweise entsteht das Thiocarbonyl-ylid 7d auch durch Umsetzung des schwefelverbriickten Dianions Id mit dem Dikation 10. Die spektrometrischen Daten der neuen Verbindungen 1,7 und 8 werden diskutiert und die "C-NMR-Daten der Thiocarbonyl-ylide mit denen der Dianion-und Dikation-sulfide verglichen. Novel Sulfur-bridged Three-membered Ring Compounds of the Type of the Dianion Sulfides and of the Thiocarbonyl YlidesReaction of the potassium salts of the thiodeltates 4a,b with the deltaines 5a,b results in the formation of novel dianion sulfide salts la-c. Thiocarbonyl ylides 7a-d and 8a-d, respectively, with cyclopropenium and deltate functions are prepared by the reaction of the thiones 6a-d with the deltaines 5a,b or of the cyclopropenium salt 9 with the potassium thiodeltate 4a. Interestingly, treatment of the sulfur-bridged dianion 1 d with the dication 10 also yields the thiocarbonyl ylide 7d. The spectroscopic data of the new compounds 1, 7, and 8 are discussed, the "C NMR data of the thiocarbonyl ylides are compared with those of the dianion and dikation sulfides.In der Reihe schwefelverbriickter Dreiringverbindungen sind Dikation-sulfide vom Typ 3 stabil und isolierbar, wenn die positiven Ladungen durch Donorfunktionen D wie z. B. Dialkylaminogruppen ausreichend delokalisiert werden konnen'*'). Die bisher unbekannten Dianion-sulfide 1 oder die Thiocarbonyl-ylide Z3) sollten bei geeigneter Substitution ebenfalls eine zur Isolierung ausreichende Stabilisierung erfahren. In 1 diirften dazu Acceptorgruppen A wie die Dicyanmethylen-oder die Cyaniminfunktion sehr gut geeignet sein. Die Ylide 2 miinten im anionischen Teil acceptor-, im kationischen Teil donatorsubstituiert sein. Wir berichten hier iiber Synthesen und spektrometrische Daten erster, in Substanz isolierbarer Vertreter beider Verbindungsklassen 1 und 2, wobei 2 Cyclopropenium-und Deltatfunktionen am Schwefel tragt, 1 die acceptorsubstituierten Deltate.
C3S 32⊖: this structural formula corresponds to the smallest possible thioxocarbon dianion, which has now been obtained in the form of several salts, e.g., 1. The X‐ray structure analysis of 1 provides useful information concerning the bonding in this dianion, which can be described in terms of delocalized π electrons.
The title compounds (III) and (VI) (stable towards light and air; discussion of 13C NMR, IR and mass spectra) are prepared by reaction of (II) with (I) to give (III) or with (V) to afford (VI).
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