Chemical Constitution and Reactivity. I. Phenyldiazonium Chloride and its Mono Substituted Derivatives

Solvolysis of o-methylbenzenediazonium tetrafluoroborate in acidic methanol-water mixtures. Further evidence for nucleophilic attack on a solvent separated aryl cation

“…Figure 1 shows a continuous increase in k o on going from k o ϭ 9.50 ϫ 10 Ϫ4 s Ϫ1 (0 % MeOH) up to k o ϭ 14.0 ϫ 10 Ϫ4 s Ϫ1 (99.6% MeOH). The k o value at 0% MeOH is in agreement with literature values of k o ϭ 9.6 ϫ 10 Ϫ4 s Ϫ1 obtained by N 2 evolution [27] at pH ϭ 1.6 -1.8 and with that of k o ϭ 10.3 ϫ 10 Ϫ4 s Ϫ1 obtained spectrophotometrically [28]. The observed increase in k o is also in agreement with published results for other dediazoniations in acidic MeOH [30].…”

“…3A) yield an identical value, k o ϭ 12.60 ϫ 10 Ϫ4 s Ϫ1 , which is equal, within experimental error, to that obtained for OMBD loss from the variation of the absorbance of the azo dye with time, Figure 3B.We also investigated the effect of added electrolytes like HCl, NaCl, and CuCl 2 on k o at different MeOH/H 2 O mixtures. Table IA shows the average values, which indicate that k o is not affected by added electrolytes, exhibiting a similar behavior as that observed for other arenediazonium ions in water [27,28].…”

“…The aim of the article is double: to expand the scope of applicability of the method to solvents other than water and to complement studies concerning the nucleophilic attack on aryl cations. We have chosen methanol as solvent and o-methylbenzenediazonium tetrafluoroborate, OMBD, as substrate because it conforms to the requirements described above about solubility, its dediazoniation mechanism in water is known [27,28] showing a convenient dediazoniation rate constant value at T ϭ 35ЊC.…”

Correlation of 13C and 15N nuclear magnetic resonance chemical shifts with polarographic reduction potentials of para-substituted benzenediazonium salts and their electronic structures

“…2 in ref. 7) may be related to the well-known and still unexplained fact that both thep-NOz and p-OCH, derivatives decompose more slowly (22) in acid than the unsubstituted salt (H > p-NO2 a p-OCH,).…”

Rates and pH-dependent product distributions of the CuCl2-catalyzed dediazoniation ofp-nitrobenzenediazonium ­tetrafluoroborate in aqueous acid

“…However, in earlier reports, the observation of non-first-order kinetics was not mentioned. [22][23][24] To clarify this problem, we investigated the kinetics and mechanism of the PNBD dediazoniation reaction in aqueous acidic solution in the presence and absence of CuCl 2 but without added reductant or ligand transfer agent. Kinetics were studied both spectrophotometrically (UV-visible) and by quenching the dediazoniation reaction with a suitable coupling agent at periodic time intervals and measuring the product yields.…”