Reaction of 3,3,3-Tribromo- and 1,3,3,3-Tetrabromo-1-nitroprop-1-enes with Aliphatic Dienes
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tion of 3,3,3-Tribromoand 1,3,3,3-Tetrabromo-1-nitroprop-1-enes with Aliphatic Dienes N. A. Anisimovaa,b,*, E. K. Slobodchikovaa, M. E. Ivanovac, and T. V. Rybalovad,e a Herzen
State Pedagogical University of Russia, St. Petersburg, 191186 Russia St. Petersburg State University of Industrial Technologies and Design, St. Petersburg, 191186 Russia c Altai State Agricultural University, Barnaul, 656049 Russia d Vorozhtsov Novosibirsk Institute of Organic Chemistry, Siberian Branch, Russian Academy of Sciences, Novosibirsk, 630090 Russia e Novosibirsk State University, Novosibirsk, 630090 Russia *e-mail: [email protected] b
Received May 11, 2020; revised May 11, 2020; accepted May 20, 2020
Abstract—3,3,3-Tribromo- and 1,3,3,3-tetrabromo-1-nitroprop-1-enes reacted with 2-methyl- and 2,3-dimethylbuta-1,3-dienes to give cyclohexene, cyclohexane, and hepta-1,5-diene derivatives containing nitro and tribromomethyl groups. The products were characterized by IR and 1H and 13C NMR spectra and X-ray diffraction data. Keywords: 3,3,3-tribromo-1-nitroprop-1-ene, cyclohexene derivatives, hepta-1,5-diene, Diels–Alder reaction, 1,4-addition
DOI: 10.1134/S1070363220080022 Cyclohexane ring is a structural fragment of many natural compounds (e.g., vitamins, terpenes, hormones, alkaloids, shikimic acid, and other practically important compounds) [1, 2] exhibiting significant biological properties (e.g., enzyme inhibitory activity [3, 4]) and used as key precursors to medicines with anticancer [5], narcotic [6, 7], and antiviral [8, 9] activities, as well as anti-HIV drug candidates [10]. A convenient and available method for the synthesis of functionalized cyclohexene derivatives is based on the Diels–Alder reaction utilizing vicinally substituted nitroalkenes with a readily modifiable group (CO2R, SO2Ph, CHlg3) as dienophiles [11, 12]. Such dienophiles have been used to obtain natural biologically active compounds, including the analgesic epibatidine [13, 14], morphine derivatives [15], and conduritols [10]. The Diels–Alder synthesis of a nitrocyclohexene containing a trihalomethyl group provides the possibility of further modification of the cyclic structure and enhancement of pharmacological activity [14]. According to published data, Diels–Alder reactions of 3,3,3-trichloro-1-nitroprop-1-ene with aliphatic dienes such as buta-1,3-diene, 2,3-dimethylbuta-1,3diene, isoprene, and piperylene requires harsh conditions
(prolonged heating in a high-boiling solvent in a sealed ampule) [16–18]. We previously showed that vicinally substituted nitroalkenes and geminal bromonitroalkenes containing trifluoromethyl and trichloromethyl groups are capable of reacting with aliphatic dienes at room temperature [19]. In this work, we studied the behavior of 3,3,3-tribromoand 1,3,3,3-tetrabromo-1-nitroprop-1-enes in reactions with 2-methyl- and 2,3-dimethylbuta-1,3-dienes, which have not been reported previously. 3,3,3-Tribromo- and 1,3,3,3-tetrabromo-1-nitroprop-1-enes 1 and 2 reacted with 2,3-dimethylbuta-1,3-dienes in benzene at room temperature
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