含窒素芳香族複素環N-オキシドに対する酸クロリドおよびシアン化物の反応(第4報) : 2位と4位に置換基のあるQuinoline N-Oxideとスルフォン酸クロリド, シアン化カリウムとの反応について

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Reaction of 2,4-disubstituted quinoline 1-oxides (Ix) with methanesulfonyl chloride and potassium cyanide in acetone-water system was attempted. As the disubstituted quinoline 1-oxides, 2,4-dimethyl-(I_2), 2-methyl-4-phenyl-(I_3), 2-ethyl-4-methyl-(I_4), and 4-methyl-2-phenyl-quinoline 1-oxide (I_5) were used. In all these compounds, the methane-sulfonyl group was introduced into the 3-position, with liberation of oxygen from the N→O group to form 2,4-disubstituted 3-(methylsulfonyl) quinolines (IV_<2-5>), though the yield varied. At the same time, liberation of oxygen from the N→O group alone occurred to form the corresponding bases. Unexpected products obtained in this reaction were 3-methyl-and 3-ethyl-4-methyl-carbostyril (V_2 and V_4) from I_2 and I_4,formed by rearrangement of the methyl or ethyl group to the 3-position, and 2-acetyl-4-methylquinoline (VI) from I_4. Introduction of arylsulfonyl group into the 3-position, similar to the above, was proved by using I_2 and benzenesulfoyl chloride or tosyl chloride. It was considered that, in this reaction, sulfonyl cyanide is formed from sulfonyl chloride and cyanide ion as the first step and that this sulfonyl cyanide took part in subsequent reactions. Therefore, reaction of I_2 with p-tosyl cyanide was attempted but formation of 3-(p-tolylsulfonyl) derivative (IV_<2t>) was not observed, though IV_<2t> was produced by the addition of potassium cyanide or sodium p-toluenesulfinate. Since the sulfinate ion is formed from sulfonyl cyanide and cyanide ion, it was assumed that sulfonyl chloride and sulfinate ion would directly take part in the formation of IV from the reaction of IX with sulfonyl chloride and potassium cyanide. This assumption was proved to be true by the formation of IV_<2t> in a good yield by the reaction of I_2 with tosyl chloride and sodium p-toluenesulfinate. Discussions were made on the process of formation of various products from this reaction.
社団法人日本薬学会の論文
1977-06-25

含窒素芳香族複素環N-オキシドに対する酸クロリドおよびシアン化物の反応(第4報) : 2位と4位に置換基のあるQuinoline N-Oxideとスルフォン酸クロリド, シアン化カリウムとの反応について

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