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A reevaluation of the Hofmann rearrangement in electron deficient systems: preparation of 2‐( 15 N)‐amino‐4,6‐dinitrotoluene and 4‐( 15 N)‐amino‐2,6‐dinitrotoluene
Author(s) -
Spanggord Ronald J.,
Clizbe Lane A.
Publication year - 1998
Publication title -
journal of labelled compounds and radiopharmaceuticals
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.432
H-Index - 47
eISSN - 1099-1344
pISSN - 0362-4803
DOI - 10.1002/(sici)1099-1344(199807)41:7<615::aid-jlcr106>3.0.co;2-b
Subject(s) - chemistry , yield (engineering) , molecule , amino acid , hydrolysis , high performance liquid chromatography , medicinal chemistry , stereochemistry , organic chemistry , computational chemistry , biochemistry , materials science , metallurgy
The Hofmann rearrangement is an excellent synthetic method to introduce amino functions into aromatic molecules; however, it becomes less efficient in electron‐deficient systems because of competitive hydrolytic reactions. This report describes the preparation of the aminodinitrotoluenes (ADNTs) 2‐( 15 N)‐amino‐4,6‐dinitrotoluene and 4‐( 15 N)‐amino‐2,6‐dinitrotoluene by developing conditions using HPLC as a reaction monitoring technique. Both ADNTs were prepared in >70% yield and >95% isotropic purity by using organic solvents and controlling pH during the formation of N‐chlorobenzamides and then performing the rearrangement. © 1998 John Wiley & Sons, Ltd.