85314-03-0Relevant academic research and scientific papers
Aryliminodimagnesium Reagents. XIV. Reactions with Nitrobenzenes Having Electronegative ortho-Substituents. Effects of Reaction Conditions on Condensation, Replacement, and Substitution
Okubo, Masao,Inatomi, Yoshito,Taniguchi, Naoki,Imamura, Kaori
, p. 3581 - 3586 (2007/10/02)
In reactions of ArN(MgBr)2 with o-MeO- and o-halo-substituted nitrobenzenes, types and yields of products were different from those in its reactions with m- and p-substituted substrates.Condensation (leading to unsymmetrical azoxy- and azobenzenes), o-substituent replacement, and nuclear substitution took place.Relative yields of products were greatly affected by substituents and reaction conditions. o-MeO and o-F favor replacement, while o-Cl, o-Br, and o-I favor substitution.Replacement and/or substitution predominate when small molar excess of reagent and low concentration are used, while condensation predominates when large molar excess of reagent and high concentration are used, which phenomenon is mechanistically discussed.
Preparations and Structures of 3-Chloro-ONN-4'-methylazoxybenzene and 4-Methoxy-ONN-4'-methylazoxybenzene
Yamamoto, Jiro,Tsuboi, Takashi,Sumi, Yasunori,Oda, Noriyasu,Fukuyama, Keiichi
, p. 3814 - 3816 (2007/10/02)
A treatment of 3-chloro-NNO-4'-methylazoxybenzene (1β) with CrO3 in acetic acid gave 3-chloro-ONN-4'-methylazoxybenzene (1α) in good yield, whereas 4-methoxy-ONN-4'-methylazoxybenzene (2α) isomerized partially to 4-methoxy-NNO-4'-methylazoxybenzene (2β) under the same conditions.The structures of 1α and 2α have been determined by X-ray analysis.
Aryliminodimagnesium Reagents. IV. The Independent Preparation of Unsymmetrically Substituted Azoxyarene Isomers and Their Deoxygenation
Okubo, Masao,Koga, Koji
, p. 203 - 207 (2007/10/02)
By use of the condensation reaction of aryliminodimagnesium reagents (ArN(MgBr)2) with nitroarenes, six symmetrical and eight unsymmetrical azoxyarenes including four pairs of isomers were prepared in 40-80percent yields.The deoxygenation reaction of the azoxyarenes by treating with five molar equivalents of p-MeOC6H4N(MgBr)2 at 55 deg C in tetrahydrofuran was also studied, and the reactivity of deoxygenation was correlated to the shift of the electronic absorption maximum of azoxyarene.
