There are three possible sites in 2-quinoxalinecarbonitrile (I) which would be attacked by a nucleophilic reagent ; (1) the ring carbon in 3-position, (2) the ring carbon in 3-position and (3) the carbon in -C≡N bond. Based on this assumption, the reaction of I with carbanion as the nucleophilic reagent was carried out. The carbanion source were various ketones (II) such as acetophenone (IIa), propiophenone (IIb), cyclopentanone (IIc), cyclohexanone (IId), acetone (IIe), diethyl ketone (IIf), methyl ethyl ketone (IIg), methyl propyl ketone (IIh), and methyl isopropyl ketone (IIi), and the reaction was carried out in benzene in the presence of sodium amide. It was thereby found that the reaction of I with IIa afforded 2-(2-quinoxalinyl)acetophenone (IIIa) and 3-(2-quinoxalinyl)-3-iminopropiophenone (IVa) corresponding to the above assumptions (1) and (3), but no product correspondihg to that of (2). In the case of IIb, IIc, and IId, the products were IIIb, IIIc, and IIId corresponding to IIIa, while in the case of IIe, IIg, IIh, and IIi, only IVe, IVg, IVh, and IVi corresponding to IVa were obtained. The reaction of I and IIf afforded 1-(2-quinoxalinyl)-2-methyl-1, 3-butanedione (Vf), considered to be formed via IVf. For the structure of IVa, e, g, h, i, tautomerism between the enamino-ketone (IV') and iminoenol (IV") forms can be considered besides the iminoketone form (IV), and IV' or IV" structure seems more likely than IV. When the so-called active methylene compound (VII) was used as the carbanion source, the reaction II with phenylacetonitrile (VIId) gave α-phenyl-2-quinoxalineacetonitrile (VIII) corresponding to the assumption (1).
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