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The synthesis of halogenated pyridines substituted at the carbon atom C‐3
Author(s) -
Sutter Peter,
Weis Claus D.
Publication year - 1987
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.5570240434
Subject(s) - chemistry , aromatization , acetic anhydride , moiety , medicinal chemistry , organic chemistry , acetic acid , carbon atom , hydrolysis , solvent , ring (chemistry) , pyridine , chloride , reactivity (psychology) , catalysis , medicine , alternative medicine , pathology
Arylation of α‐methyleneglutaronitrile (MGN) occurred when arylamines, aminopyridines and 3‐aminothiophene were treated with alkylnitrites and copper(I) chloride in dimethyl methylphosphonate (DMMP) solutions. Results from this study exemplified the synthetic advantage of DMMP as a solvent in Meerwein reactions with an olefin of low reactivity, yielding 1‐aryl‐2 chloro‐2,4‐dicyanobutanes, and its 3‐pyridyl‐ and thiophen‐3‐yl analogues. Partial hydrolysis, followed by subsequent ring closure of the substituted 2,4‐dicyanobutanes to 2,6‐piperidinediones (glutaric acid imides) was effected with a solution of sulfuric acid in acetic acid. The aromatization of the substituted 2,6‐piperidinediones with phosphorus oxychloride in the presence of hexamethylphosphoric acid triamide (HMPT) yielded the 2,6‐dichloropyridine moiety substituted at the carbon atom C‐3.