13125-93-4

Upstream product

• 540-37-4 p-aminoiodobenzene 
• 14454-14-9 N-(4-iodophenyl)hydroxylamine 
• 636-98-6 p-nitrobenzene iodide 
• 5122-99-6 4-iodophenylboronic acid 
• 108921-73-9 p-iodonitrosobenzene 

Downstream Products

• 478953-22-9 4-(4-iodo-phenylazo)-benzoic acid 
• 34946-97-9 [2-(4-iodo-phenyl)-4,4-diphenyl-[1,2]oxazetidin-3-ylidene]-p-tolyl-amine 
• 19618-18-9 1,2-bis(4-iodophenyl)diazene oxide 
• 21650-53-3 (E)-1,2-bis(4-iodophenyl)diazene 
• 636-98-6 p-nitrobenzene iodide 
• 131319-20-5 (E)-4-((4-iodophenyl)diazenyl)aniline 
• 1176334-15-8 C₁₈H₁₃IN₂ 

Relevant academic research and scientific papers

Understanding Mechanistic Differences between 3-Diazoindolin-2-Imines and N-Sulfonyl-1,2,3-Triazoles in the Rh2(II)-Catalyzed Reactions with Nitrosoarenes

The employment of α-iminometallocarbenes to construct valuable N-containing compounds has attracted significant research interest. Herein, the nucleophilic addition of nitrosoarenes with the α-imino rhodium carbene species (I), which is derived from Rh2(II)-catalyzed denitrogenation of 3-diazoindolin-2-imines, to produce synthetically useful 2-iminoindolin-nitrones is described. Mechanistically, the N-attack of nitrosoarenes with the carbene site of I is proposed. For the analogous Rh2(II)-catalyzed reaction of nitrosoarenes with N-sulfonyl-1,2,3-triazoles reported by Li and co-workers (Org. Lett. 2014, 16, 6394), however, the O-attack of nitrosoarenes with the carbene site of α-imino rhodium carbene species (II) is more favorable to occur than the N-attack. The subsequent transformation to yield the product of N-acylamidines is rationalized based on computational studies. The mechanistic differences for the reactions of nitrosoarenes with α-imino rhodium carbene species I and II are discussed.

Synthesis of Di(hetero)arylamines from Nitrosoarenes and Boronic Acids: A General, Mild, and Transition-Metal-Free Coupling

The synthesis of di(hetero)arylamines by a transition-metal-free cross-coupling between nitrosoarenes and boronic acids is reported. The procedure is experimentally simple, fast, mild, and scalable and has a wide functional group tolerance, including carbonyls, nitro, halogens, free OH and NH groups. It also permits the synthesis of sterically hindered compounds.

Metal-Free Sequential C(sp2)-H/OH and C(sp3)-H Aminations of Nitrosoarenes and N-Heterocycles to Ring-Fused Imidazoles

Hydrogen bond assisted ortho-selective C(sp2)-H amination of nitrosoarenes and subsequent α-C(sp3)-H functionalization of aliphatic amines is achieved under metal-free conditions. The annulation of nitrosoarenes and 2-hydroxy-C-nitroso compounds with N-heterocycles provides a facile excess to a wide range of biologically relevant ring-fused benzimidazoles and structurally novel polycyclic imidazoles, respectively. Nucleophilic aromatic hydrogen substitution (SNArH) was found to be preferred over classical SNAr reaction during the C(sp2)-H amination of halogenated nitrosoarenes.

Crystal disordering and organic solid-state reactions

This work is the extension of our preliminary communication about the relationship between the change in the solid-state structure and the chemical reaction in a crystal. The investigation is a case study about the nature of the adiabatic organic solid-st

Mechanochemically induced cross-dimerizations of nitrosobenzenes. Kinetics and solid-state isotope effects

Mechanical treatment (milling) of crystals of aromatic nitroso dimers (azodioxides) induces their dissociation and cross-dimerizations. The mechanisms of these processes are discussed on the basis of kinetic studies and the solid-state 15 N kinetic isotope effect, which is measured for the first time. By comparison with analogous processes in cocrystals and in melts, it appears that the reactions follow similar mechanism in which the surface deformations play the crucial role. The system can also be used as a model for a more general conceptual study of solid-state reaction mechanisms. Copyright

Nitrosation of aryl and heteroaryltrifluoroborates with nitrosonium tetrafluoroborate

Organotrifluoroborates have emerged as an alternative to toxic and air- and moisture-sensitive organometallic species for the synthesis of functionalized aryl and heteroaryl compounds. It has been shown that the trifluoroborate moiety can be easily converted into a variety of different substituents in a late synthetic stage. In this paper, we disclose a mild, selective, and convenient method for the ipso-nitrosation of organotrifluoroborates using nitrosonium tetrafluoroborate (NOBF4). Aryl- and heteroaryltrifluoroborates were converted into the corresponding nitroso products in good to excellent yields. This method proved to be tolerant of a broad range of functional groups.

Mechanosynthesis of nitrosobenzenes: A proof-of-principle study in combining solvent-free synthesis with solvent-free separations

Mechanochemical Oxone oxidation of selected para-substituted anilines was used as a rapid and solvent-free route to nitrosobenzenes; besides avoiding bulk solvents and short reaction times, this method exploits high vapour pressures of nitrosobenzenes for the solvent-free separation of the product by sublimation, demonstrating an entirely solvent-free route to chemical synthesis and product isolation. The Royal Society of Chemistry.

Nitrosobenzene cross-dimerization: Structural selectivity in solution and in solid state

Possibility of nitrosobenzenes to form dimeric molecular structures (azodioxides) is used as a model for intermolecular selectivity investigations in solution as well as in solid state. Cross-dimerization of different combinations of p- and m-substituted nitrosobenzene pairs was studied by variable temperature 1H NMR, solid-state NMR (CP MAS), IR, and ab initio calculations. It is evident that p-nitronitrosobenzene behaves nonselectively because it forms dimers with all the studied nitrosobenzene partners. In contrast, p-methoxynitrosobenzene in most cases does not form dimers. The evidence that ability to form dimers is different in solution than in the solid state can be explained by influence of molecular arrangements in the crystal lattice.

α,α-difluorophosphonomethyl azobenzene derivatives as photoregulated phosphoamino acid analogs. 1. Design and synthesis

A series of novel, photoregulated phosphoamino acid analogs based on an azobenzene core bearing an α,α-difluoromethylphosphonate as a hydrolytically stable phosphate isostere have been prepared with N-Fmoc protection for use in peptide synthesis. Classes of reagents analogous to both phosphotyrosine and phosphoserine/threonine were prepared by a common route employing a nitrosoarene/aniline condensation to form the azo linkage and the Cu(I)-promoted coupling of an iodoarene with (diethylphosphono)difluoromethyl cadmium bromide (Burton's method) to introduce the phosphonate moiety.

Structural investigations of C-nitrosobenzenes. Part 2. NMR studies of monomer-dimer equilibria including restricted nitroso group rotation in monomers

Energy barriers associated with rotation of nitroso groups in monomeric nitrosobenzene and eleven monomeric substituted nitrosobenzenes in solution have been measured by total 1H NMR bandshape analysis. ΔG? (298.15 K) values for the rotations are in the range 31-41 kJ mol-1. The values for 4-substituted compounds correlate well with the Hammett σp+ parameter for the substituent. The experimental energy barrier for nitrosobenzene is compared with theoretical calculations. Monomerdimer equilibria of these compounds in solution have been investigated, with ΔH, ΔSominus; and ΔGominus; data calculated for the dissociation of both Z- and E- azodioxy dimers to monomers. Kinetic data, based on time-dependent and two-dimensional exchange spectroscopy (2D-EXSY) NMR measurements, have been obtained for the dissociation of 3-methylnitrosobenzene and 3,5-dimethylnitrosobenzene dimers. Energy profiles for the ground and transition states of both dimers and monomers (including exchange between both their rotameric forms) are discussed.