21650-60-2

Upstream product

• 873-77-8 (4-chlorphenyl)magnesium bromide 
• 106-47-8 4-chloro-aniline 
• 104-94-9 4-methoxy-aniline 
• 108-95-2 phenol 
• 17333-85-6 4-chlorophenyldiazonium salt 
• 2703-27-7 4-[(E)-(4-chlorophenyl)diazenyl]phenol 
• 74-88-4 methyl iodide 
• 932-98-9 1-chloro-4-nitroso-benzene 
• 77-78-1 dimethyl sulfate 

Relevant academic research and scientific papers

Azo Dyes: New Palladium- and Copper-Catalysed Coupling Reactions on an Old Template

The elaboration of azo dyes using a variety of transition-metal-catalysed reactions (Stille, Heck, Ullmann, and Suzuki couplings) is reported. This methodology has been applied to the synthesis of functionalised coumarin azo dye conjugates, substrates which may find potential application in the development of new sensors.

Zr(OH)4-Catalyzed Controllable Selective Oxidation of Anilines to Azoxybenzenes, Azobenzenes and Nitrosobenzenes

The selective oxidation of aniline to metastable and valuable azoxybenzene, azobenzene or nitrosobenzene has important practical significance in organic synthesis. However, uncontrollable selectivity and laborious synthesis of the expensive required catalysts severely hinders the uptake of these reactions in industrial settings. Herein, we have pioneered the discovery of Zr(OH)4 as an efficient heterogeneous catalyst capable of the selective oxidation of aniline, using either peroxide or O2 as oxidant, to selectively obtain various azoxybenzenes, symmetric/unsymmetric azobenzenes, as well as nitrosobenzenes, by simply regulating the reaction solvent, without the need for additives. Mechanistic experiments and DFT calculations demonstrate that the activation of H2O2 and O2 is primarily achieved by the bridging hydroxyl and terminal hydroxyl groups of Zr(OH)4, respectively. The present work provides an economical and environmentally friendly strategy for the selective oxidation of aniline in industrial applications.

The selective synthesis ofN-arylbenzene-1,2-diamines or 1-arylbenzimidazoles by irradiating 4-methoxy-4′-substituted-azobenzenes in different solvents

The solvent-controllable photoreaction of 4-methoxyazobenzenes to afford 1-aryl-1H-benzimidazoles orN-arylbenzene-1,2-diamines has been studied. The irradiation of 4-methoxyazobenzenes in DMF containing 0.5 M hydrochloric acid providedN2-aryl-4-methoxybenzene-1,2-diamines as the major product, while irradiation in acetal containing 0.16 M hydrochloric acid led to 1-aryl-6-methoxy-2-methyl-1H-benzimidazoles as the major product. A possible reaction mechanism explaining the selectivity was also discussed.

Easily Accessible, Highly Potent, Photocontrolled Modulators of Bacterial Communication

External control of bacterial communication—quorum sensing—allows for the regulation of a multitude of biological processes. Herein, we describe the development of a new synthetic methodology, as well as the characterization, photoisomerization, and biological evaluation of a privileged series of novel photoswitchable quorum-sensing agonists and antagonists. The presented method allows for the rapid and convenient synthesis of previously unknown photoswitchable agonists with up to 70% quorum-sensing induction and inhibitors reaching up to 40% inhibition, which significantly extends the level of photocontrol over bacterial communication achieved before. Remarkably, for the lead photoswitchable agonist, a >700-fold difference in activity was observed between the irradiated and non-irradiated forms, which allows for antagonism-to-agonism switching upon exposure to light, showing levels of control unprecedented in photopharmacology. Finally, utilizing this system, we were able to regulate toxin production in Pseudomonas aeruginosa with light. Photopharmacology is an emerging approach aimed at the regulation of biological function with light. Herein, the application of molecular photoswitches allows for the reversible switching between two distinct structural states of bioactive compounds. Bacterial communication (quorum sensing) is an interesting target for photopharmacology, from the perspective of both clinical and basic research, because of its implications for pathogenicity of bacteria and complex biological mechanism of action. By the novel synthesis and application of photoswitchable modulators, we were able to reversibly control bacterial communication with light. Remarkably, one of our lead compounds allows the control of bacterial communication with very high selectivity, switching from a quorum-sensing inhibitor to a quorum-sensing activator upon irradiation with light, which was further exemplified by the control of quorum-sensing-regulated toxin production in Pseudomonas aeruginosa. By applying the photopharmacological approach, bacterial communication can be controlled with light through the application of photoswitchable modulators. Interestingly, one of the lead photoswitchable modulators of bacterial communication, presented herein, shows a remarkable (>700-fold) difference in activity between the non-irradiated and irradiated states. The photoresponsive quorum-sensing modulators can be used to control toxin production in Pseudomonas aeruginosa and have a promising outlook as next-generation research tools.

First use of p-tert-butylcalix[4]arene-tetra-O-acetate as a nanoreactor having tunable selectivity towards cross azo-compounds by trapping silver ions

p-tert-Butylcalix[4]arene-tetra-O-acetate was established for the first time as a member of the nanoreactor series, even without having any -OH group. The nano range distribution of this nanoreactor was ascertained by DLS, SEM and TEM studies. The capability of this cavitand towards hosting amines in a competitive manner generates a new green pathway for cross coupling of aromatic amines to give the corresponding azo-compounds. In this context, using p-tert-butylcalix[4]arene-tetra-O-acetate as a nanoreactor and silver nitrate as a catalyst, we got the cross azo-compound in good to excellent yields in the eco-friendly solvent water. This green methodology is also applicable for the synthesis of respective homo-compounds.

Phenyliodine(III) diacetate (PIDA) mediated synthesis of aromatic azo compounds through oxidative dehydrogenative coupling of anilines: Scope and mechanism

An efficient and environmentally benign method has been developed for the synthesis of symmetrical and unsymmetrical aromatic azo compounds through phenyliodine(III) diacetate (PIDA) mediated oxidative dehydrogenative coupling of anilines in high yields.

Preparation of diazenes by electrophile C-coupling reactions of dry arenediazonium o-benzenedisulfonimides with Grignard reagents

The diaryldiazenes (19 examples) and aryl(tertbutyl)diazenes (3 examples) 3 were prepared by electrophilic C-coupling reactions of dry arenediazonium o-benzenedisulfonimides 1 with Grignard reagents. The reactions were carried out in anhyd THF at -78°C un