A semi-target analytical method for quantification of OH-PCBs in environmental samples.

Hydroxylated polychlorinated biphenyls (OH-PCBs) are oxidative metabolites of PCBs and residuals found in original Aroclors. OH-PCBs are known to play a role as genotoxicants, carcinogens, and hormone disruptors, and therefore it is important to quantify their presence in human tissues, organisms, and environmental matrices. Of 837 possible mono-OH-PCBs congeners, there are only ~ 70 methoxylated PCB (MeO-PCB) standards commercially available. Hence, a semi-target analytical method is needed for unknown OH-PCBs. The mass concentrations of these unknowns are sometimes determined by assuming the peak responses of other available compounds. This can bias the results due to the choices and availabilities of standards. To overcome this issue, we investigated the peak responses of all commercially available MeO-PCB standards with gas chromatography (GC) coupling with triple quadrupole (QqQ) mass spectrometry (MS) system, with positive electron impact (EI) ionization at 20-70 eV in selected ion monitoring (SIM) mode. We found correlations between the relative peak responses (RRFs) and the number of chlorine (#Cl) in the molecules of MeO-PCBs. Among the studied models, the quadratic regression of #Cl is the most suitable model in the RRF prediction (RRF = ß1 × #Cl^2 + ß0) when the peak responses are captured at 30 eV. We evaluated the performance of the model by analyzing 12 synthesized MeO-PCB standards and a PCB-contaminated sediment collected from a wastewater lagoon. We further demonstrate the utility of the model using a different chromatography column and GC-EI-MS system. We found the method and associated model to be sufficiently simple, accurate, and versatile for use in quantifying OH-PCBs in complex environmental samples.

Intramolecular (4 + 2) cycloaddition of aryl-1-aza-2-azoniaallene salts: A practical approach to highly sterically-congested polycyclic protonated azomethine imines.

We report an improved two-step reaction sequence that gives tricyclic protonated azomethine imine products containing a 1,2,3,4-tetrahydrocinnoline scaffold in high yield. This sequence involves the oxidation of aryl hydrazones with TFAA-activated DMSO to give the corresponding α-trifluoroacetoxyazo products, which react readily with TMSOTf to give 1-aza-2-azoniaallene salt intermediates that undergo intramolecular (4+2) cycloadditions with pendent alkenes. This reaction sequence is more general, more practical and more environmentally friendly than our initially reported method. The cycloaddition provides exceptionally sterically-hindered products in high yield.

Mechanism and Dynamics of Intramolecular C-H Insertion Reactions of 1-Aza-2-azoniaallene Salts.

The 1-aza-2-azoniaallene salts, generated from α-chloroazo compounds by treatment with halophilic Lewis acids, undergo intramolecular C-H amination reactions to form pyrazolines in good to excellent yields. This intramolecular amination occurs readily at both benzylic and tertiary aliphatic positions and proceeds at an enantioenriched chiral center with retention of stereochemistry. Competition experiments show that insertion occurs more readily at an electron-rich benzylic position than it does at an electron-deficient one. The C-H amination reaction occurs only with certain tethers connecting the heteroallene cation and the pendant aryl groups. With a longer tether or when the reaction is intermolecular, electrophilic aromatic substitution occurs instead of C-H amination. The mechanism and origins of stereospecificity and chemoselectivity were explored with density functional theory (B3LYP and M06-2X). The 1-aza-2-azoniaallene cation undergoes C-H amination through a hydride transfer transition state to form the N-H bond, and the subsequent C-N bond formation occurs spontaneously to generate the heterocyclic product. This concerted two-stage mechanism was shown by IRC and quasi-classical molecular dynamics trajectory studies.