Kinetics of solvolysis of 1‐acetyl‐4‐(1‐ethoxycarbonyl‐1‐cyano) methylene‐1,4‐dihydroquinoline in undried DMSO‐d 6· formation of Acetic Anhydride as an intermediate

The kinetics of solvolysis of the title compound (QAc) in undried DMSO‐d 6 to give 4‐(1‐ethoxycarbonyl‐1‐cyano)methylquinoline (QH) and HOAc at ambient temperature were investigated by 1 H nmr spectrometry. With a limited excess of water the solvolysis follows a three‐step process of \documentclass{article}\pagestyle{empty}\begin{document}$ {\rm QAc} + {\rm H}_2 {\rm O}\mathop \to \limits^{k_1} {\rm QH} + {\rm HOAc}, $\end{document} , and \documentclass{article}\pagestyle{empty}\begin{document}$ {\rm Ac}_{\rm 2} {\rm O} + {\rm H}_2 {\rm O}\mathop \to \limits^{k_3} {\rm 2\,HOAc}, $\end{document} where k 2 > k 1 and k 3 < k 1 . Addition of pyridine‐d 5 to the reaction mixture markedly catalyzes the overall solvolysis, while addition of CF 3 CO 2 D to the reaction mixture simplifies the kinetics to pseudo first‐order in [QAc] with k = 4.3 × 10 −3 min −1 .