Dihydrobenzoxazines and tetrahydroquinoxalines by a tandem reduction-reductive amination reaction

被引:44
作者
Bunce, RA [1 ]
Herron, DM [1 ]
Hale, LY [1 ]
机构
[1] Oklahoma State Univ, Dept Chem, Stillwater, OK 74078 USA
关键词
D O I
10.1002/jhet.5570400611
中图分类号
O62 [有机化学];
学科分类号
070303 ; 081704 ;
摘要
A tandem reduction-reductive amination reaction has been applied to the synthesis of 3,4-dihydro-2H-1,4-benzoxazines and 1-acetyl-1,2,3,4-tetrahydroquinoxalines. The nitroketones required for the benzoxazine ring closures were prepared by (A) alkylation of the anion derived from 2-nitrophenol with an allylic halide or (B) nucleophilic aromatic substitution of an allylic alkoxide on 2-fluoro-1-nitrobenzene followed by ozonolysis. Precursors for the quinoxalines were prepared by alkylation of the anion of 2-nitroacetanilide with an allylic halide followed by ozonolysis. Catalytic hydrogenation of the nitroketones using 5% palladium-on-carbon in methanol then gave the target heterocycles by a reduction-reductive amination sequence. The N-methyl derivatives for both ring systems were easily prepared by adding 5-10 equivalents of aqueous formaldehyde prior to the reduction. The dihydrobenzoxazines were isolated in high yield following purification by chromatographic methods; tetrahydroquinoxalines were isolated in a similar manner and possessed differentiated functionality on the two nitrogens.
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页码:1031 / 1039
页数:9
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