Abstract: | It is shown that the heptalene‐4,5‐dicarboxylates 5 react with their Me group at C(1) with N,N‐dimethylformamide dimethyl acetal or other acetals of this type in N,N‐dimethylformamide (DMF) to give the corresponding 1‐(E)‐2‐(N,N‐dialkylamino)ethenyl]‐substituted heptalene‐4,5‐dicarboxylates 8a – 8e as well as 8k and 8i in good yields (Table 1). In a similar manner, the 1‐(E)‐2‐pyrrolidinoethenyl]‐substituted heptalene‐5‐carboxylates 8f – h were synthesized from the corresponding heptalene‐carboxylates 10 – 12 , carrying a CHO, CN, or (E)‐2‐(methoxycarbonyl)ethenyl group at C(4) (Table 1). All new heptalenes with the π‐donor and π‐acceptor groups at C(1) and C(4), respectively, exhibit a strongly enhanced heptalene band I in the spectral region of 450 – 500 nm in MeCN (Table 7 and Figs. 4 – 7), whereby the specific position is dependent on the π‐donor quality of the N,N‐dialkylamino substituent at C(2′) and the π‐acceptor property of the group at C(4). The position of heptalene band I is also strongly solvent‐dependent as is demonstrated in the case of heptalene 8i (Table 9). A good linear correlation with the CT band of 1‐(diethylamino)‐4‐nitrobenzene or (E)‐4‐(dimethylamino)‐β‐nitrostyrene (Figs. 11 and 12) characterizes the heptalene band I also as an electronic CT transition. Irradiation into this band of 8i leads, as observed in other cases (cf. 1]), to a double‐bond shift in the heptalene moiety (→ 8′i ; Figs. 8 – 10). On warming in solution, 8′i is converted quantitatively to 8i . |