Formation of the Meisenheimer spiro adduct of N-(2,4,6-trinitrophenyl)alanine methylamide and its rearrangement to 2-amino-N-methyl-N-(2,4,6-trinitrophenyl)propanamide
1986 ◽
Vol 51
(9)
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pp. 1972-1985
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Keyword(s):
N-(2,4,6-trinitrophenyl)alanine methylamide (I) undergoes base-catalyzed cyclization in methanol to give the spiro adduct II. In aniline-anilinium chloride buffers, the spiro adduct is protonated at the oxygen atom of 2-nitro group to give the neutral compound III. In 4-bromoaniline buffers or by action of methanolic hydrogen chloride, the compound III is opened to E and Z isomers of 2-amino-N-methyl-N-(2,4,6-trinitrophenyl)propanamide hydrochloride (IV). The rate-limiting step of cyclization of compound Z-IV to compound III consists in the isomerization Z-IV → E-IV. At higher pH values (acetate buffers), the rate-limiting step is gradually changed to the isomerization of 2-amino-N-methyl-N-(2,4,6-trinitrophenyl)propanamide (Z-V → E-V).
1990 ◽
Vol 55
(5)
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pp. 1216-1222
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Keyword(s):
2003 ◽
Vol 16
(6)
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pp. 311-317
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Keyword(s):
1978 ◽
Vol 39
(02)
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pp. 496-503
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Keyword(s):
1965 ◽
Vol 30
(3)
◽
pp. 622-628
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