Fluoranthene Derivatives. II. The Reaction of Acenaphthylene with Butadiene Derivatives¹

Synthesis of Novel Fluoranthene-Based Conformationally Constrained α-Amino Acid Derivatives and Polycyclic Aromatics via the Diels–Alder Reaction

“…A possible route to α-amino acid derivatives 7 and 8 was envisioned involving ethyl isocyanoacetate (14) 14 and diethyl acetamidomalonate (15). Alternatively, αamino acid derivative 9 could be derived by Diels-Alder reaction of fluoranthene-fused sultine 10 and methyl 2-acetamidoacrylate (16) involving the transient diene intermediate 10A. Our strategy may be extended toward the synthesis of fluoranthene-fused polycyclic compound 12 by a Diels-Alder reaction involving sultine intermediate 10, which can act as a latent diene equivalent 10A (Scheme 1).…”

“…The required 8,9-dimethylfluoranthene (17) was prepared by following the literature procedure. 15,16 Although, Clar and Stephen 17a reported the synthesis of 8,9-bis(bromomethyl)fluoranthene (13) by a different route 17 with limited data (melting point and CHN analysis only), we prepared 8,9-bis(bromomethyl)fluoranthene (13) by following a slightly modified route with the aid of N-bromosuccinimide by adopting the radical bromination of an aromatic methyl group. Toward the synthesis of α-amino acid derivatives, such as 7-9, and polycyclic derivatives, the synthesis of the key building block 8,9-bis(bromomethyl)fluoranthene (13) seems to be a non-trivial task.…”

“…Further, sultine 10 was heated at 100°C to deliver the corresponding sulfone 11 in 74% yield. Later, the sultine 10 was treated with methyl 2-acetamidoacrylate (16) in toluene at reflux for 43 hours to furnish the desired product, aminotetralincarboxylic acid 9 (Atc) derivative in 50% yield (Scheme 3). Next, the 8,9-bis(bromomethyl)fluoranthene (13) was reacted with ethyl isocyanoacetate (14) in the presence of potassium carbonate in refluxing acetonitrile under phasetransfer conditions to give the alkylated product, which was directly treated with concentrated hydrochloric acid in absolute ethanol to generate the desired amino ester.…”

XXVIII.—The Synthesis of 7-Substituted Fluoranthenes

“…(MS. received October 13, 1961. Read December 4, 1961 THE synthesis of 7-substituted fluoranthenes has been effected in only three instances, namely, the 7-methyl-, 7-methoxy-, and 7-phenyl-derivatives (Bergmann 1948;Kloetzel and Mertel 1950;Tucker and Whalley 1952;and Stubbs and Tucker 1954). We have explored a new route and have thus succeeded in synthesizing 7-chloro-and 7-bromo-fluoranthene.…”

Polymers and Copolymers of Acenaphthylene

“…Acenaphthylene and butadiene are known to undergo a Diels-Alder condensation under suitable conditions to give tetrahydrofluoranthene (Bergmann, 1948 ;Kloetzel & Mertel, 1950). Linear copolymers are obtained by emulsion polymerization.…”