Report on 2-bromonaphthalene

Introduction

2-Bromonaphthalene (Figure 1) was synthesized by the reaction of 2-naphthol with bromine in the presence of triphenylphosphorus in 70% -80% yield. It is mainly used as pharmaceutical intermediates and dye raw materials, and used in Suzuki cross coupling reaction to synthesize biaryl compounds. It is a hazardous chemical, which may cause harm if swallowed or contacted with eyes. It is necessary to wear protective equipment during operation.

Report 1:Mechanisms of dioxin formation

Brominated hydrocarbons are the most commonly used flame retardants. Materials containing brominated hydrocarbons are frequently disposed in municipal and hazardous waste incinerators as well as being subjected to thermal reaction in accidental fires. This results in the potential for formation of brominated dioxins and other hazardous combustion byproducts. In contrast to chlorinated hydrocarbons, the reactions of brominated hydrocarbons have been studied only minimally. As a model brominated hydrocarbon that may form brominated dioxins, we studied the homogeneous, gas-phase pyrolytic thermal degradation of 2-bromophenol in a 1-cm i.d., fused-silica flow reactor at a concentration of 90 ppm, with a reaction time of 2.0 s, and over a temperature range of 300 to 1000 degrees C. Observed products included dibenzo-p-dioxin (DD), 1-monobromodibenzo-p-dioxin (1-MBDD), 4-monobromodibenzofuran (4-MBDF), dibenzofuran (DF), naphthalene, bromonaphthalene, 2,4- and 2,6-dibromophenol, phenol, bromobenzene, and benzene. These results are compared and contrasted with previous results reported for 2-chlorophenol. At temperatures lower than 700 degrees C, formation of 2-bromophenoxyl radical, which decomposes through CO elimination to form a bromocyclopentadienyl radical, forms naphthalene and 2-bromonaphthalene through radical recombination/rearrangement reactions. However, unlike the results for 2-chlorophenol, where naphthalene is the major product, DD becomes the major product for the pyrolysis of 2-bromophenol. The formation of DD and 1-MBDD are attributed to radical-radical reactions involving 2-bromophenoxyl radical with the carbon- (bromine) centered radical and the carbon- (hydrogen) centered radical mesomers of 2-bromophenoxyl radical, respectively. The potential product, 4,6-dibromodibenzofuran (4,6-DBDF) for which the analogous product, 4,6-dichlorodibenzofuran (4,6 DCDF), was observed in the oxidation of 2-chlorophenol, was not detected. This is attributed to the pyrolytic conditions of our experiments (e.g., shorter reaction times and higher temperatures) that favor reaction intermediates that form DD and 1-MBDD.[1]

Report 2: MPDS degradation

Polycyclic aromatic hydrocarbons (PAHs) commonly coexist in contaminated sites, posing a significant threat to ecosystem. Strains that degrade a wide range of substrates play important roles in bioremediation of contaminated environment. In this study, we reveal that Pseudomonas brassicacearum MPDS was able to remove 31.1% naphthalene of 500 mg/kg from soil within 2 d, while its relative abundance decreased significantly on Day 20, indicating its applicable potential in soil remediation. In addition to naphthalene, dibenzofuran, dibenzothiophene, and fluorene as reported previously, strain MPDS is able to degrade carbazole, phenanthrene, pyrene, and 2-bromonaphthalene. Moreover, NahA from strain MPDS has multi-substrate catalytic capacities on naphthalene, dibenzofuran, dibenzothiophene, phenanthrene, and 2-bromonaphthalene into dihydrodiols, while converts fluorene and carbazole into monohydroxy compounds according to GC-MS analysis. This study provides further insights into the exploration of soil remediation by strain MPDS and the mining of enzymes involved in the degradation of PAHs.[2]

Report 3: Complexes containing α-cyclodextrin and bromonaphthalene derivatives

Ultraviolet absorption spectra, NMR spectra, and phosphorescence measurements were used to confirm that alpha-cyclodextrin (CD) and 2-bromo-6-beta-D-glucopyranosidylnaphthalene (BGN) form only a binary complex and to characterize its properties. The binding constant for the CD·BGN complex was found to be 886±24 M-1 and 770±110 M-1 from NMR and UV absorbance measurements, respectively. Comparison of spectral properties revealed the CD.BGN complex to be binary and complexes containing CD and n-alkoxy (n-alkanoloxy) derivatives of 2-bromonaphthalene (N) to be of higher order, notably ternary. A red shift was observed in the UV absorption spectra of the CD₂·2-bromonaphthalene complexes. The absence of a hydroxyl hydrogen atom on the naphthalene ring of N molecules made it impossible for hydrogen bond formation to a glucosidic oxygen in the CD cavity to be the cause of the red shift. The similar red shifts reported herein and for the ternary complexes of CD with 2-naphthol and 2-bromo-6-hydroxynaphthalene (BOHN) indicated that hydrogen bond formation between the hydroxyl hydrogen and glucosidic oxygen atom might not be the cause of the red shift for the latter guest molecules, as has been proposed previously. This result emphasizes the caution necessary in using UV absorption spectral data as evidence for hydrogen bond formation in molecular complexes containing CD.[3] 

References

1. Evans CS, Dellinger B. Mechanisms of dioxin formation from the high-temperature pyrolysis of 2-bromophenol. Environ Sci Technol. 2003;37(24):5574-5580. doi:10.1021/es034387s

2. Chen Z, Hu H, Xu P, Tang H. Soil bioremediation by Pseudomonas brassicacearum MPDS and its enzyme involved in degrading PAHs. Sci Total Environ. 2022;813:152522. doi:10.1016/j.scitotenv.2021.152522

3. Park GB, Brown DM, Schuh MD. Binary and ternary complexes containing alpha-cyclodextrin and bromonaphthalene derivatives: a note of caution in interpreting UV absorption spectral data. J Phys Chem B. 2006;110(45):22510-22516. doi:10.1021/jp064287j

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