29666-87-3Relevant academic research and scientific papers
Electrooxidative conversion of aldehyde and ketone phenylhydrazones into the methoxy(phenylazo) alkanes
Okimoto, Mitsuhiro,Nagata, Yuji,Takahashi, Yukio
, p. 1447 - 1448 (2003)
Several aldehyde and ketone phenylhydrazones were converted into the corresponding methoxy(phenylazo)alkane derivatives by electrochemical oxidation in MeOH.
The Nature of Azo-Substituted Carbocations: N-N π-Electron Stabilization versus Nitrogen Nonbonding Electron Stabilization
Creary, Xavier
, p. 2241 - 2254 (2021/04/12)
Computational and experimental studies reveal two different modes of cation stabilization by the phenylazo group. The first mode involves a relatively weak conjugative interaction with the azo π-bond, while the second mode involves an interaction with the nitrogen nonbonding electrons. The 4-phenylazo group is slightly rate-retarding in the solvolysis of cumyl chloride and benzyl mesylate derivatives but rate-enhancing in the solvolysis of α-CF3 benzylic analogs. The phenylazo group can become a potent electron-donating group in cations such as [Me2C─N═N─Ph]+. Nonbonding electron stabilization can be strong enough to offset the very powerful γ-silyl stabilization. In aromatic cyclopropenium and tropylium cations, the demand for stabilization is quite low, and the mode of phenylazo stabilization reverts back to the less-effective π-stabilization. The solvolysis of cis-4-phenylazo benzyl mesylate is faster than that of trans-4-phenylazo benzyl mesylate. Products formed suggest a stepwise ionization, cation isomerization, and nucleophile capture mechanism. Computational studies indicate a vanishingly small barrier for the isomerization of the cis-cation intermediate to the trans-cation.
Electrochemical formation of methoxy- and cyano(phenylazo)alkanes from aldehyde and ketone phenylhydrazones
Okimoto, Mitsuhiro,Takahashi, Yukio,Kakuchi, Toyoji
, p. 2057 - 2063 (2007/10/03)
Several aldehyde and ketone phenylhydrazones were electrooxidized in MeOH. Electrooxidation in the presence of KI or tetraethylammonium p-toluenesulfonate as the supporting electrolyte afforded the corresponding methoxy(phenylazo)alkanes, whereas electrooxidation in the presence of KI, NaCN, and HOAc afforded the cyano(phenylazo)alkanes.
