2000
DOI: 10.1039/b003079l
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Revisiting the reactions of nucleophiles with arenediazonium ions: dediazoniation of arenediazonium salts in aqueous and micellar solutions containing alkyl sulfates and alkanesulfonates and an ab initio analysis of the reaction pathway

Abstract: Dediazoniation of 2,4,6-trimethylbenzenediazonium tetrafluoroborate, 1-ArN 2 BF 4 (for the z-Ar compounds described in this paper, z refers to the length of the carbon chain of the substituent at C4 of the benzene ring), in aqueous solutions containing sodium methyl sulfate, NaMeSO 4 , or sodium methanesulfonate, NaMeSO 3 , yields 2,4,6-trimethylphenol, 1-ArOH, 2,4,6-trimethylphenyl methyl sulfate, 1-ArOSO 3 Me and 2,4,6-trimethylphenyl methanesulfonate, 1-ArO 3 SMe, respectively. The relative yields of 1-ArO … Show more

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Cited by 41 publications
(48 citation statements)
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References 37 publications
(53 reference statements)
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“…These results are consistent with previous work indicating that the observed product distribution reflects the concentrations of nucleophiles in their immediate environment (i.e., in the first solvation shell of ArN 2 ϩ ions). [8,26] Diazo ethers of the general structure ArNϭNOR (with R ϭ alkyl, aryl) are rarely formed as stable products. [3,10,33,34] The diazo ether formally derived from 1-naphthol and the benzenediazonium ion, for example, is sensitive to acid and base as well as to light.…”
Section: Resultsmentioning
confidence: 99%
See 1 more Smart Citation
“…These results are consistent with previous work indicating that the observed product distribution reflects the concentrations of nucleophiles in their immediate environment (i.e., in the first solvation shell of ArN 2 ϩ ions). [8,26] Diazo ethers of the general structure ArNϭNOR (with R ϭ alkyl, aryl) are rarely formed as stable products. [3,10,33,34] The diazo ether formally derived from 1-naphthol and the benzenediazonium ion, for example, is sensitive to acid and base as well as to light.…”
Section: Resultsmentioning
confidence: 99%
“…The homolytic dediazoniation pathway requires an electron transfer to the arenediazonium ions, which can be accomplished in different ways, [2,3] including reductive methods at an electrode [4Ϫ7] or by employment of nucleophilic anions or nucleophilic neutral molecules such as alcohols. [8,9] The variety of methods and reducing agents that can be employed to generate intermediate aryl radicals (Ar · ) and the multiplicity of steps open to radical reactions pH favors homolytic dediazoniation, with quantitative conversion into the reduction product toluene being obtained at pH Ն 6 (4MBD), indicating that a turnover from the heterolytic to the homolytic mechanisms is taking place under experimental conditions under which insignificant amounts of EtO − or OH − should be present in solution. The obtained Sshaped profiles suggest that the initiation process of the homolytic pathway is the result of the formation of a highly unstable transient diazo ether complex and not by direct electron transfer from the solvent (EtOH) to the arenediazonium ions as is currently believed.…”
Section: Introductionmentioning
confidence: 99%
“…4B), NOH is again the main dediazoniation product but conversion to NOH is less than quantitative. This phenomenon has already been observed in dediazoniations taking place in SDS micellar systems 38,39 and is attributed to a competing reaction between the arenediazonium ions and the sulfate head groups of the surfactant, yielding the corresponding aryl alkyl sulfate, which is unstable and further hydrolyzes leading to the formation of aryl sulfates (ArOSO − 3 ), which are not detected by reversed‐phase HPLC because of its ionic nature 12. Because no other peaks that might be attributed to radical pathways, i.e., NH, were observed in the chromatograms, we assumed, as Cuccovia et al 38 and Bravo et al 39 did in the past, that the formation of the unknown product is a competitive reaction with an unidentified component, which leads to a reduction in the total observed yields, which are calculated on the basis of the initial PNBD concentration.…”
Section: Discussionmentioning
confidence: 76%
“…Several groups investigated (and still they do) the effects of micellar and macromolecular systems on dediazoniations, and two major lines of research are evident. On the one hand, the basic physical organic aspects of the reactions have been explored 12–15. Alternatively, new methods to estimate interfacial compositions of weak nucleophiles in colloidal interfaces were developed based on the unique characteristics of dediazoniation reactions 4–6.…”
Section: Introductionmentioning
confidence: 99%
“…Hydrophobicity of arenediazonium ion and charge of the micelle are believed to be the most important factors affecting the localization of ions in the micellar system. Positively charged hydrophilic arenediazonium ions do not associate with cationic micelles [32] whereas they are incorporated into negatively charged SDS micelles and their preferential location is very close to the micellar surface. At the same time no evidence of tight ion-pairs formation between diazonium ions and anionic micelles was found [24].…”
Section: Resultsmentioning
confidence: 98%