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Alkyl nitrate nitration of active methylene compounds. Nitration of 1‐methyl4‐piperidone, 1‐methyl‐2‐pyrrolidinone and 1,3‐dimethyl‐2‐pyrrolidinone
Author(s) -
Feuer Henry,
Blecker Lamarr R.,
Jans Robert W.,
Frost John W.
Publication year - 1979
Publication title -
journal of heterocyclic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.321
H-Index - 59
eISSN - 1943-5193
pISSN - 0022-152X
DOI - 10.1002/jhet.5570160314
Subject(s) - nitration , chemistry , yield (engineering) , medicinal chemistry , ring (chemistry) , methylene , nitro , potassium nitrate , alkyl , nitrate , potassium , organic chemistry , materials science , metallurgy
The reaction of 1‐methyl‐4‐piperidone ( 1 ) with amyl nitrate in the potassium tert ‐butoxidetetrahydrofuran system gave dipotassium 5‐methyl‐2‐oxo‐1,3‐piperidinedinitronate ( 4 ) in 78% yield. Similar treatment of 1‐methyl‐2‐pyrrolidinone ( 2 ) afforded potassium 3‐methyl‐2‐oxopyrrolidinenitronate ( 7 ) in 85% yield. In contrast, the nitration of 1,3‐dimethyl‐2‐pyrrolidinone ( 3 ) led to opening of the lactam ring with the formation of amyl 2‐aza‐2‐methyl‐5‐nitrohexanoate ( 10 ) in 40% yield. Acidification of disalt 4 did not cause ring opening but gave the dipolar ion of 1‐methyl‐3‐nitro 4‐hydroxy‐5‐ aci ‐nitro‐Δ 3 ‐tetrahydropyridinium (6).