A simple direct procedure for the regiospecific preparation of chloro aromatic compounds

Bay, Elliott; Timony, Peter E.; Leone-Bay, Andrea

doi:10.1021/jo00247a042

Cited by 12 publications

(1 citation statement)

References 3 publications

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“…The reaction of 5 with triphenyloxyphosphorus dichloride prepared in situ by mixing phosphorus pentachloride with phenol afforded tetraphenyloxyphosphorus monochloride, which was further decomposed at high temperature to give 7 . The chlorodenitration of 7 following an optimized procedure reported by Bay et al was possible using phenyltetrachlorophosphorane prepared in situ by the reaction of chlorine gas with dichlorophenyl phosphine. However, it was necessary to lower the originally reported temperature from 170 to 150 °C and to keep the reaction for a longer time in order to minimize any potential evaporation of the formed product (bp = 174 °C).…”

Section: Resultsmentioning

confidence: 99%

Synthesis and In Situ Behavior of 1,4- and 2,5-(¹³C) Isotopomers of p-Phenylenediamine in Reconstructed Human Epidermis Using High Resolution Magic Angle Spinning NMR

Srour

Gosset

Moussallieh

et al. 2022

Chem. Res. Toxicol.

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Para-phenylenediamine (PPD) has been classified as a strong skin allergen but when it comes to toxicological concerns, benzoquinone diamine (BQDI), the primary oxidation derivative of PPD, is frequently considered and was shown to covalently bind nucleophilic residues on model peptides. However, tests in solution are far from providing a reliable model as the cutaneous metabolism of PPD is not covered. We now report the synthesis of two 13 C substituted isotopomers of PPD, 1,4-( 13 C)p-phenylenediamine 1 and 2,5-( 13 C)pphenylenediamine 2, and the investigation of their reactivity in reconstructed human epidermis (RHE) using high resolution magic angle spinning (HRMAS) NMR technique. RHE samples were first treated with 1 or 2 and incubated for 1 to 48 h. Compared to the control, spectra clearly showed only the signals of 1 or 2 gradually decreasing with time to disappear after 48 h of incubation. However, the culture media of RHE incubated with 1 for 1 h and 24 h, respectively, showed the presence of both monoacetylated-and diacetylated-PPD as major products.Therefore, the acetylation reaction catalyzed by N-acetyltransferase (NAT) enzymes appeared to be the main process taking place in RHE. With the aim of increasing the reactivity by oxidation, 1 and 2 were treated with 0.5 equiv. H2O2 prior to their application to RHE and incubated for different times. Under these conditions, new peaks having close chemical shifts to those of PPDcysteine adducts previously observed in solution were detected. Under such oxidative conditions, we were thus able to detect and quantify cysteine adducts in RHE (maximum of 0.2 nmol/mg of RHE at 8 h of incubation) while no reaction with other nucleophilic amino acid residues could be observed.

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Section: Resultsmentioning

confidence: 99%

Synthesis and In Situ Behavior of 1,4- and 2,5-(¹³C) Isotopomers of p-Phenylenediamine in Reconstructed Human Epidermis Using High Resolution Magic Angle Spinning NMR

Srour

Gosset

Moussallieh

et al. 2022

Chem. Res. Toxicol.

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Preparation of Halides and Sulfonates

1992

Compendium of Organic Synthetic Methods

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Preparation of Halides and Sulfonates

Smith

2009

Compendium of Organic Synthetic Methods

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A simple direct procedure for the regiospecific preparation of chloro aromatic compounds

Cited by 12 publications

References 3 publications

Synthesis and In Situ Behavior of 1,4- and 2,5-(¹³C) Isotopomers of p-Phenylenediamine in Reconstructed Human Epidermis Using High Resolution Magic Angle Spinning NMR

Synthesis and In Situ Behavior of 1,4- and 2,5-(¹³C) Isotopomers of p-Phenylenediamine in Reconstructed Human Epidermis Using High Resolution Magic Angle Spinning NMR

Preparation of Halides and Sulfonates

Preparation of Halides and Sulfonates

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A simple direct procedure for the regiospecific preparation of chloro aromatic compounds

Cited by 12 publications

References 3 publications

Synthesis and In Situ Behavior of 1,4- and 2,5-(13C) Isotopomers of p-Phenylenediamine in Reconstructed Human Epidermis Using High Resolution Magic Angle Spinning NMR

Synthesis and In Situ Behavior of 1,4- and 2,5-(13C) Isotopomers of p-Phenylenediamine in Reconstructed Human Epidermis Using High Resolution Magic Angle Spinning NMR

Preparation of Halides and Sulfonates

Preparation of Halides and Sulfonates

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Product

Resources

About

Synthesis and In Situ Behavior of 1,4- and 2,5-(¹³C) Isotopomers of p-Phenylenediamine in Reconstructed Human Epidermis Using High Resolution Magic Angle Spinning NMR

Synthesis and In Situ Behavior of 1,4- and 2,5-(¹³C) Isotopomers of p-Phenylenediamine in Reconstructed Human Epidermis Using High Resolution Magic Angle Spinning NMR