2011
DOI: 10.1021/jp203771c
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Photoinduced Rearrangement of AromaticN-Chloroamides to Chloroaromatic Amides in the Solid State: Inverted ΠN–ΣNOccupational Stability of Amidyl Radicals

Abstract: We report a solid-state photochemical rearrangement reaction by which aromatic N-chloroamides exposed to UV light or sunlight are rapidly and efficiently converted to chloroaromatic amides. The course, the intermediate (nascent chlorine vs dichlorine) and the outcome of the reaction depend on the excitation (exposure time, wavelength, and intensity) and on inherent structural factors (the directing role of the substituents and, as demonstrated by the different reactivity of two polymorphs of N-chlorobenzanilid… Show more

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Cited by 7 publications
(4 citation statements)
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“…It has, for example, been shown recently that N-phenylacetamidyl radicals possess a σ ground state if appropriately substituted at the ring moiety. 29 The calculated RSE values for phenylaminyl radicals correlate well with Brown substituent constants (σ p + ), in line with earlier observation. 30b The linear relationship (r = 0.994) of the RSE and Brown's σ p + values displayed in Fig.…”
Section: Resultssupporting
confidence: 90%
“…It has, for example, been shown recently that N-phenylacetamidyl radicals possess a σ ground state if appropriately substituted at the ring moiety. 29 The calculated RSE values for phenylaminyl radicals correlate well with Brown substituent constants (σ p + ), in line with earlier observation. 30b The linear relationship (r = 0.994) of the RSE and Brown's σ p + values displayed in Fig.…”
Section: Resultssupporting
confidence: 90%
“…Interestingly, the N-Cl bond of 1a (1.763 A ˚) was determined to be relatively longer than those of certain N-chloro species (1.700-1.715 A ˚) that were reported to homolytically dissociate under photolytic conditions. 51 With the recognition of these structural aspects, the photostability of 1a was tested under visible light irradiation in MeCN (Figure 2B). Despite the comparably longer N-Cl bond length, 1a was found to be inert to homolysis under the photo conditions, in which the stability might have resulted from the structural rigidity or the incapability to absorb the light energy.…”
Section: Resultsmentioning
confidence: 99%
“…A range of aliphatic aldehydes could also be efficiently amidated in reaction with 1a (1.2 equiv) in the presence of benzoic acid additive (15 mol %): linear (7,(38)(39)(40)(41) and sterically more demanding branched aldehydes (42)(43)(44), as well as cyclic substrates (45)(46)(47)(48)(49)(50)(51), were all feasible. As in the case of benzaldehydes, labile functional groups such as alkyl bromide (39) and a,b-unsaturated olefinic units (50-51) were found to be compatible.…”
Section: Reaction Scopesmentioning
confidence: 99%
“…The chloride concentration in the membranes treated with 0, 20 ppm and 50 ppm NaOCl was never higher than the sum of the sodium and two times the calcium concentration, suggesting that the chloride was probably present as sodium or calcium chloride contaminations. The low level of chloride in the membrane that was actively chlorinated with 1 ppm could be associated with photochemical decomposition of the chloramide (N-Cl) species [50], as no contaminating metal cations were detected in this sample. Additionally, it was not possible to deconvolute the Cl-peaks into an additional binding partner, i.e.…”
Section: Surface Chlorine Analysis Via Wd-xrf and Xps 32mentioning
confidence: 89%