1.3-Donor/Donor-Substituted Allenes, VII1ll. -Allenecarboxanilides by Transallenation or [2.3]/[3.3]-SigmatropicRearrangements -Building Blocks with Versatile Intra-and Intermolecular Synthetic Potential*The reaction of 1,3-bis(alkylarylamino)-1,3-diethoxyallenes 1, 2 with disubstituted malonyl chlorides 3 leads to N,N-dialkyl-N,N-diarylallene-1,l-dicarboxamides 4, 5, and 2H-pyran-2,4(3H)-diones 6, 7, respectively, with a transallenation reaction being favoured in the case of allene 1. Thermal tandem cyclisation of allene-1,l-dicarboxanilide 4c via 2-quinolone 8 affords phenanthridone 9. Spontaneous acylcycloalkanelcycloenol ether isomerisation of spirane 6b gives pyrane 12. Thermally induced (Z)-anilinoacrylic acidlquinolone cyclisation of pyranes 6a, 12, and 7 leads to 4-quinolones 11,13, and 14. Propargyl THP ether 15 reacts with carbamoyl chloride 16 to yield alkinol-N-phenylanilides 17. Alkinol 17a reacts with sulfinyl chloride 18 to yield sulfinic ester 19, which on heating undergoes a [2.3]-sigmatropic rearrangement to N-phenyl-lsulfonylallene-1-carboxanilide 20. Reaction of alkinols 17 with sulfenyl chlorides 21 or chlorophosphanes 23, followed by [2.3]-sigmatropic shift, affords N-phenyl-1-sulfinyl-22 and Nphenyl-1-phosphorylallene-1-carboxanilides 24, respectively. Alkinyl ketene acetal intermediates 26 are formed starting from alkinol 17 a and orthoesters 25. Spontaneous (3.31-sigmatropic rearrangement of 26 gives N-phenylallene-l-carboxanilides 27. Intramolecular Diels-Alder (IDA) reactions of the allene-1-carboxanilides 27 lead to (2.2.2lbicycles 28. Contrarily, the IDA intermediates of 20 b and 24 further isomerize to the [3.2.l]bicycles 29 and 30. The allenyl sulfoxides 22 readily undergo Michael-type reactions with CH-acidic compounds 31 to give ally1 sulfoxides 32. Among these, only 32d can be isolated, whereas 32a-c spontaneously rearrange in a fourstep reaction cascade to butenolides 33a-c. A Michael-type reaction of (diethoxyphosphory1)allenes 24 with whydroxy ketones 34 followed by a Horner-Emmons reaction leads to alkylidene-dihydro-furans 35, which isomerize in the presence of a base to yield furans 36. Analogously, allenes 24 react with 2-hydroxybenzaldehydes 37 or 2-pyrrole-/2-imidazole derivatives 40 to form alkylidenechromenes 38 and pyrrolizines/ pyrroloimidazoles 41, respectively. Benzopyrylium salts 39 are accessible from chromenes 38 and perchloric acid.Die Umsetzung von 1,3-Bis(alkylarylamino)-1,3-diethoxyallenen mit disubstituierten Malonylchloriden liefert

Mit disubstituierten Malonylchloriden 7 erhiilt man aus den leicht darstellbaren iJ-Diethoxy-1,3-bis(anilino)allenen 6 in Abhangigkeit vom Raumanspruch der Substituenten R' und R2 durcb Umalleniencng die AUendianiGde 9 bnv. die Dioxopyrane 8 und 10.Wichtige Folgeprodukte von 10 und 8 b sind die Pyranoderivate 11s (R6ntgenstntkturrUIalyse) und 13. Durcb intramolekulare Diels-Alder-Reaktion von 9c und daraullblgende Isomerisierung

ChemInform Abstract Depending on the bulkiness of the substituents and the reaction temp., the disubstituted malonyl chlorides (I), (IV) react with the conveniently accessible allene (II) by transallenation to give the products (III) or (V). Whereas the AlCl3-induced isomerization of the known analogue (VI) of (IIIc) gives the pyranopyrane (VII) (X-ray analysis: P21/n; Z=4), the pyranoquinolinedione (VIII) is formed by thermolysis of (IIIc). Thermal reactions of (Va), (Vb) yield the products (IX), (X) or (XI). The reaction of the diacid chloride (XII) with (II) leads directly to the cyclized product (XIII). The attempt to vinylogize the transallenation fails.

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