Reactions of 1,4-quinone N,N'-dibenzenesulfonylimines, 1,4-quinones, and 1,4-quinone N,N'-dibenzoylimines with secondary diazo compounds. Structures of alleged arocyclopropenes

Abstract

1,4‐Benzochinon‐N,N′‐dibenzolsulfonylirnin (I) und das Naphthochinon‐Analogon (IV) reagieren mit Diphenyldiazomethan (II) zu den Addukten (III) bzw. (V).

Developments in cycloproparene chemistry

“…Treatment of 43 with fert-butoxide affords 39b directly but in low yield. 32 The formation of 1,6methano [10]annulene from 44 under essentially the same reaction conditions has been described,35 and an analogous path involving a bridgehead olefin is likely to operate; base-catalyzed epimerization at C12 is pre- Billups procedure is unlikely to succeed when the endothermic migration of a tetrasubstituted olefinic linkage is required (cf. 45 -* 46) and/or when loss of HX can occur in two distinct ways.…”

“…Except for 39 and 41a (see below) each of these compounds results from a precursor in which the 7,7-dichlorobieyclo[4.1.0]hept-3-enyl moiety is in place. The [10]annulene derivatives 39a and 39b are formed from 42 and 43, respectively. While 42 may be regarded as SCHEME VI sumed to lead to 39b as the thermodynamically more stable isomer.…”

“…Scheme XIII depicts a range of cycloadditions that exemplify the value of 1 in the synthesis of bridged annulenes. Thus 1 reacts with butadiene84 to give the dihydro [10]annulene 108 in addition to 109, the product of diradical trapping. It reacts with aryl nitrile oxides to yield the heterocyclic propellanes 110,96 with a-pyrone to give l,6-methano [10]annulene 111,84 with 1,2,4-triazines to afford the 3,8-methanoaza [10]annulenes 112 (several from reaction at high pressure),97 and with l,2,4,5-tetrazine-3,6-dicarboxylate to provide the diazotetraene 113.98 This last product84 has now been isolated and characterized as the bisnorcaradiene98 rather than its ring-opened valence bond isomer.…”

“…Thus 1 reacts with butadiene84 to give the dihydro [10]annulene 108 in addition to 109, the product of diradical trapping. It reacts with aryl nitrile oxides to yield the heterocyclic propellanes 110,96 with a-pyrone to give l,6-methano [10]annulene 111,84 with 1,2,4-triazines to afford the 3,8-methanoaza [10]annulenes 112 (several from reaction at high pressure),97 and with l,2,4,5-tetrazine-3,6-dicarboxylate to provide the diazotetraene 113.98 This last product84 has now been isolated and characterized as the bisnorcaradiene98 rather than its ring-opened valence bond isomer. Furthermore, bridged ten-electron [9]annulenes 114 and 116 emanate" from reaction of 1 with mesoionic oxathiazolines and dithiolanes, the latter via the isolable norcaradiene 115. The formation of compounds [111][112][113] proceeds by way of thermally labile cycloadducts that undergo decarboxylation or deazetation under the reaction conditions.…”

N,N-[(Z,Z)-7,7-Diphenylbicyclo[4.1.0]hept-3-ene-2,5-diylidene]dibenzenesulfonamide

“…The title compound was reported (Mustafa & Kamel, 1953) to form a substituted benzocyclopropene, (1), which would have been possibly the earliest synthesis (Anet & Anet, 1964;Vogel et al, 1965) of this type of unique structure. On the basis mainly of spectroscopic evidence (Pinkus & Tsuji, 1974;Jones et al, 1974), the product was instead suggested to be a bicylic structure, (2), of a three-membered ring fused to a sixmembered one [Halton, 1973; since this review was published before the papers by Pinkus & Tsuji (1974) and Jones et al (1974) appeared, these two references, which deal with the correction of the report by Mustafa & Kamel (1953), do not appear in the review; the numbering of the bicyclic compound without substituents is given in the Halton reference] {named by Chem. Abstr.…”