
TY  - JOUR
A1  - McCallum, Peter B. W. 
A1  - Grimmett, M. Ross 
A1  - Blackman, Allan G. 
A1  - Weavers, Rex T. 
T1  - Reaction of Imidazoles with Cyanogen Bromide: Cyanation at N 1 or Bromination at C 2?
JF  - Australian Journal of Chemistry
JO  - Aust. J. Chem.
Y1  - 1999
VL  - 52
IS  - 3
SP  - 159
EP  - 166
KW  - 
UR  - https://doi.org/10.1071/C98105 
N2  - The reaction in acetonitrile solution of a number of imidazoles(1H-, 1-methyl-, 2-methyl-, 4-methyl-, 1,2-, 1,4- and1,5-dimethyl-, 1-ethyl-, 1-benzyl- and 1-butyl-imidazole) and imidazolecomplexes(&#91;Co(NH3)5(imH)&#93;(ClO4)3,&#91;Co(NH3)5(im)&#93;(ClO4)2 and&#91;Co(NH3)5(1-Meim)&#93;(ClO4)3) with BrCN has beenstudied. Those imidazoles bearing an N-alkyl substituent and having a hydrogenat C2 react to give the 2-bromo products, while the N-H imidazoles react togive N-cyano derivatives. The product(s) from thereaction of 1,2-dimethylimidazole with BrCN could not be characterized. Of thecomplexes, only&#91;Co(NH3)5(im)&#93;(ClO4)2 reacts, giving the 2-bromoproduct. Our observations suggest a lone pair on a ring nitrogen atom isnecessary for an imidazole to react with BrCN, and a possible mechanism issuggested. The X-ray structure of 2-methylimidazole-1-carbonitrile isreported. Crystal data (&#8211;143&#176;C) forC5H5N3:monoclinic, P21/c, a10&#183;201(5), b 7&#183;110(3),c 7&#183;227(3) &#197;, &#946; 100&#183;47(2)&#176;,V 515&#183;4(4) &#197; 3 , Z 4,dcalcd 1&#183;380 gcm&#175;3 . Refinement of the structure converged withR1 0&#183;0444 for 1183reflections with Fo &#62;4F(Fo) andwR2 0&#183;1259 for all 1278data. 
ER  -

