Molecular rearrangements. 19. Thermolysis and photolysis of N-arylbenzenesulfonamides

Badr, M. Z. A.; Aly, M. M.; Fahmy, A. M.

doi:10.1021/jo00336a033

Cited by 33 publications

(9 citation statements)

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“…Haas et al reported that sulfonamides, such as 2, undergo photolysis in Et 2 O or MeOH to give an aniline derivative and a photo-Fries rearrangement-type product (Scheme 1). [7,8] They reported that S À N bond cleavage (a photocleavage) is a radical step that affords a radical pair, resulting in the formation of the aniline derivative. It was proposed that the a photocleavage of 2 proceeds via excited triplet states.…”

Section: Introductionmentioning

confidence: 99%

Photolysis of the Sulfonamide Bond of Metal Complexes of N‐Dansyl‐1,4,7,10‐Tetraazacyclododecane in Aqueous Solution: A Mechanistic Study and Application to the Photorepair of cis,syn‐Cyclobutane Thymine Photodimer

Aoki¹,

Tomiyama²,

Kageyama³

et al. 2009

Chemistry An Asian Journal

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Sulfonamide constitutes a ubiquitous functional group that is frequently used in organic chemistry, analytical chemistry, and medicinal chemistry. We report herein on the photolysis of a dansylamide moiety of 1-dansyl-1,4,7,10-tetraazzacyclododecane (N-dansylcyclen, L(2)) in the presence of a zinc(II) ion in aqueous solution. By potentiometric pH titrations, the complexation constant for the 1:1 complex of L(2) and Zn(2+), log K(s)(ZnL(2)), in aqueous solution at 25 degrees C with I = 0.1 (NaNO(3)) was determined to be 6.5+/-0.1. The structure of the ZnL(2) complex was confirmed by single-crystal X-ray diffraction analysis. During fluorescence titrations of L(2) with Zn(2+) (irradiation at 308 or 350 nm) in aqueous solution at pH 7.4 (10 mM HEPES with I = 0.1 (NaNO(3))) and 25 degrees C, considerable enhancement in fluorescence emission of the Zn(2+) complex of L(2) (ZnL(2)) was observed, while metal-free L(2) exhibited only a negligible emission change upon UV irradiation. It was revealed that this emission enhancement arose from the photoinduced cleavage of a sulfonylamide moiety in ZnL(2), yielding the Zn(2+)-cyclen complex and 5-dimethylaminonaphthalene-1-sulfinic acid, which has a greater quantum yield (Phi) for fluorescence emission than that of L(2) and ZnL(2). For comparison, the photolysis of N-(1-naphthalenesulfonyl)cyclen (L(3)) and its Zn(2+) complex (ZnL(3)) under the same conditions (irradiation at 313 nm) gave the corresponding sulfonate (1-naphthylsulfonate). We also describe the results of a photoreversion reaction of cis,syn-cyclobutane thymine photodimer (T[c,s]T) utilizing the photolysis of ZnL(2) and ZnL(3).

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Section: Introductionmentioning

confidence: 99%

Photolysis of the Sulfonamide Bond of Metal Complexes of N‐Dansyl‐1,4,7,10‐Tetraazacyclododecane in Aqueous Solution: A Mechanistic Study and Application to the Photorepair of cis,syn‐Cyclobutane Thymine Photodimer

Aoki¹,

Tomiyama²,

Kageyama³

et al. 2009

Chemistry An Asian Journal

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“…93,94) The aqueous photolysis of asulam produced sulfanilic acid as the main product by the N-S bond cleavage, together with p-formylaminoaniline and a carbamate derivative of 1,4-benzenediamine.…”

Section: Photo-induced Bond Cleavage 311 Carboxylic Acid Derivativmentioning

confidence: 99%

Direct photolysis mechanism of pesticides in water

Katagi

2018

Journal of Pesticide Science

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Photodegradation is one of the most important abiotic transformations for pesticides in the aquatic environment, and the high energy of sunlight causes characteristic reactions such as bond scission, cyclization, and rearrangement, which are scarcely observed in hydrolysis and microbial degradation. This review deals with direct photolysis via excitation of a pesticide by absorbing natural or artificial sunlight in order to know its basic photochemistry, and indirect photolysis meaning either sensitization by dissolved organic matters or oxidation by reactive oxygen species is basically excluded. Several experimental approaches including spectroscopic techniques together with theoretical calculations are first discussed from the viewpoint of the reaction mechanisms in direct photolysis. Then, the typical photoreactions of pesticides are summarized by chemical classes and/or functional groups and discussed as far as possible in relation to their mechanisms.

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“…Interestingly, upon prolonged storage, these dihydropyridones, such as 17, undergo isomerization to the corresponding C(5)-sulfonyl products, such as 28 (isolated as a single diastereoisomer), without significant loss of enantiopurity (Scheme 5). [30] This sulfonyl transfer also .…”

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confidence: 92%

Dihydropyridones: Catalytic Asymmetric Synthesis, N‐ to C‐Sulfonyl Transfer, and Derivatizations

et al. 2012

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Molecular rearrangements. 19. Thermolysis and photolysis of N-arylbenzenesulfonamides

Cited by 33 publications

References 0 publications

Photolysis of the Sulfonamide Bond of Metal Complexes of N‐Dansyl‐1,4,7,10‐Tetraazacyclododecane in Aqueous Solution: A Mechanistic Study and Application to the Photorepair of cis,syn‐Cyclobutane Thymine Photodimer

Photolysis of the Sulfonamide Bond of Metal Complexes of N‐Dansyl‐1,4,7,10‐Tetraazacyclododecane in Aqueous Solution: A Mechanistic Study and Application to the Photorepair of cis,syn‐Cyclobutane Thymine Photodimer

Direct photolysis mechanism of pesticides in water

Dihydropyridones: Catalytic Asymmetric Synthesis, N‐ to C‐Sulfonyl Transfer, and Derivatizations

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