Alkylation and oxidation of 6,7-dihydro-6-methyl-5H-dibenzo(b,g)(1,5)thiazocine. Selective oxidation of the sulfide moiety by transannular participation of the amino group.
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概要
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6,7-Dihydro-6-methyl-5<I>H</I>-dibenzo[<I>b</I>,<I>g</I>][1,5]thiazocine (<B>7</B>) was prepared by cyclization of the corresponding amino alcohol using thionyl chloride in acetonitrile. Methylation of <B>7</B> gave <I>N</I>,<I>N</I>-dimethyl derivative (<B>8</B>) as the sole product. Treatment of <B>7</B> with various oxidizing reagents, however, afforded the corresponding sulfoxide (<B>9</B>) and/or <I>N</I>-oxide (<B>13</B>), and sulfone (<B>14</B>) depending on the kind of reagent. Oxidation of <B>7</B> with sodium periodate furnished <I>N</I>-oxide (<B>13</B>) in 72% yield as a major product along with sulfoxide (<B>9</B>) in 12% yield, while <B>9</B> was obtained as a major product (76%) by oxidation with sodium hypochlorite together with a small amount of methoxysulfonium derivative (<B>15</B>) in aqueous methanol. The acceleration in oxidation of <B>7</B> compared with diphenyl sulfide as well as production of <B>15</B> is ascribed to the transannular participation of the amino group with the chlorosulfonio group or intermediacy of a sulfurane. In addition, structural features of <B>9</B> and <B>15</B> have been investigated by means of <SUP>1</SUP>H NMR and evidence for the transannular interaction between the two heteroatoms is presented.
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