Specific features of the chemical behavior of acetylenic derivatives of benzocrown ethers |
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Authors: | S. V. Klyatskaya E. V. Tretyakov S. F. Vasilevsky |
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Affiliation: | (1) Institute of Chemical Kinetics and Combustion, Siberian Branch of the Russian Academy of Sciences, 3 ul. Institutskaya, 630090 Novosibirsk, Russian Federation |
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Abstract: | 4"-Ethynylbenzo-12-crown-4 (8), 4"-ethynylbenzo-15-crown-5 (9), and 4"-ethynylbenzo-18-crown-6 (10) were synthesized by cross-coupling of the corresponding aryl iodides 1—3 with 2-methylbut-3-yn-2-ol (4a) followed by the retro-Favorsky cleavage of the resulting carbinols. Unlike the corresponding benzo-12-crown-4 derivative (5a), the cleavage of tertiary acetylenic alcohols of benzo-15-crown-5 (6a) and benzo-18-crown-6 (7a) requires more than one molar equivalent of KOH. Aminoalkylation of crown ether 8 gives Mannich bases, independently of the reaction conditions and the nature of amine. The aminomethylation of acetylenic crown ethers 9 and 10 with paraform—piperidine (morpholine) in the presence of CuCl yields 1,4-disubstituted buta-1,3-diynes (19, 20) rather than Mannich bases. |
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Keywords: | benzocrown ethers alkynes the retro-Favorsky reaction the Mannich reaction Frank— Meister— Hay modification crown effect |
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