PMC

Previous bioconjugation work with benzene diazonium ions but has been limited primarily to in vitro use. This work focuses on developing a delivery method for benzene diazonium ions so that they may be used to study proteins in their native environment and the biochemical processes of live cells.

Reaction conditions: diazonium salt 1b (0.5 mmol), heteroarene 1a–h (0.5–5.0 mmol), MeCN/H₂O (9:1, 2 mL), EY-Na₂ (1 mol %), λ = 510 nm, T = 20 °C, and t = 4–21 h. ^b A mixture of several regioisomers.
A mixture of several regioisomers.

Coupling reaction of 1 with benzene diazonium chloride.

Compound 1 coupling reaction with benzene diazonium chloride and forms A, B, and C.

Decomposition of the diazonium salt 1 a upon irradiation at 450–475 nm with no additive, benzene or α‐methylstyrene (3 a).

The FTIR spectra of 4-([phenylsulfonyl] oxy) benzene diazonium chloride 4. FTIR: Fourier transform infrared

The method of affinity labeling of the nAChR using p-(trimethylammonium) benzene diazonium difluoroborate (TDF) with E. electricus electroplaque (reproduced from []).

Synthesis of final compounds 248a-f []; Conditions and reagents: i) HCl/H₂O, reflux (3h); ii) substituted benzene diazonium chlorides, EtOH, CH₃COONa.

Schematic of the electron transfer chemistry between graphene and 4 nitro benzene diazonium tetrafluoroborate.

Visible‐light‐induced cysteine arylation with benzene diazonium salts as aryl radical precursors. The reaction was demonstrated on a single amino acid, on dipeptides, and on a large peptide. TsOH=toluenesulfonic acid.

Schematic representation of covalent functionalization of a MOR zeolite. Benzene diazonium derivatives (electrophile) are covalently grafted to negatively charged bridging oxygen atoms of micropore walls (nucleophile) via a nucleophilic substitution reaction. N₂ (blue) and Na⁺BF₄⁻ are generated as the byproducts. Organoiodide can be used as the grafting agent instead of diazonium derivatives. For clarity, a sodium cation (yellow) is displayed in the structure adapted with permission from []. © 2021 Wiley-VCH GmbH.

The crystal structures of SO₂‐loaded SIFSIX‐1‐Cu (a) and SIFSIX‐2‐Cu‐i (b). Adapted with permission from . Copyright 2018 John Wiley and Sons. (c) Crystal structures of UiO‐66 analogues with nitration and diazonium ion formation in the benzene ring. Reproduced with permission from . Copyright 2016 John Wiley and Sons. (d) The synthesis protocol and adsorption processes of MOF-based fibrous membranes. Reproduced with permission from . Copyright 2019 Royal Society of Chemistry.

Misra and Dhar synthesized the two formazan derivatives 13 and 14 () by coupling of the corresponding hydrazones each with benzene diazonium salt and screened them for their antiviral activity against vaccinia virus and Ranikhet disease virus in a stationary culture of chorioallantoic membrane of chick embryo. The results revealed that the two compounds were found to exhibit significant activity 87% and 83%, respectively against the Ranikhet disease virus. However no activity against vaccinia virus could be observed .

Synthesis of KAUST-PI-1 (a). (i) benzene diazonium chloride, (CH₂)₂Cl₂, 80 °C, 4 h. (ii) BBr₃, CH₂Cl₂, 3 h. (iii) 4,5-dichlorophthalonitrile, K₂CO₃, N,N-dimethylformamide (DMF), 80 °C, 10 h. (iv) KOH, C₂H₅OH/H₂O, reflux 10 h. (v) acetic anhydride, reflux 12 h. vi. diamine (TMPD or TMBZ), m-cresol, isoquinoline, 200 °C, 4 h. Geometrically optimized KAUST-PI-1 demonstrating contorted, ribbon-like growth and enhanced three-dimensionality afforded by the 9,10-diisopropyl-triptycene (b). Reproduced from Reference [].

TG‐GC‐MS spectra. Top: total ion chromatogram (TIC) of three SWCNT‐PhI samples with low (blue, c(diazonium)=0.003 m), medium (green, c(diazonium)=0.021 m) and high (black, c(diazonium)=0.333 m) degree of functionalization. Bottom: MS spectra of benzene (t _R=5.2 min) and iodobenzene (t _R=10.8 min).

Covalent patterning of graphene with a nanoscale patterning resolution. (A) Schematic demonstration of the colloidal lithography method to generate covalently formed nanocorrals on the HOPG substrate for confined molecular self-assembly. Panel adapted with permission from ). Copyright: American Chemical Society. (B) Covalent patterning of graphitic substrates with the assistance of electrochemically in situ-generated products and nanobubbles as the template. Panel adapted with permission from ). Copyright: American Chemical Society. (C) Schematic illustration of covalent patterning on graphitic surfaces via the pre-assembled monolayer of p-(n-octadecyloxy) benzene diazonium, followed by electrochemical activation. Panel adapted with permission from ). Copyright: American Chemical Society. (D) Schematic illustration of covalent patterning of HOPG using self-assembled monolayers of alkanes with tunable length as templates and corresponding STM images with Fourier transforms. Panel adapted with permission from ). Copyright: American Chemical Society.

Synthesis of Protected Triazabutadiene, 3