Hydroperoxides and aryl diazonium salts as reagents for the functionalization of non-activated olefins

Hydroperoxides, olefins, and arenediazonium salts selectively combine to give azo compounds via an iron(II)-mediated three-component reaction. Starting with a fragmentation liberating acetic acid, the hydroperoxides act as radical source and the diazonium ions as nitrogen-centered radical scavengers.     

Diazonium Salts as Grafting Agents and Efficient Radical‐Hydrosilylation Initiators for Freestanding Photoluminescent Silicon Nanocrystals

The reactivity of diazonium salts towards freestanding, photoluminescent silicon nanocrystals (SiNCs) is reported. It was found that SiNCs can be functionalized with aryl groups by direct reductive grafting of the diazonium salts. Furthermore, diazonium salts are efficient radical initiators for SiNC hydrosilylation. For this purpose, novel electron‐deficient diazonium salts, highly soluble in nonpolar solvents were synthesized. The SiNCs were functionalized with a variety of alkenes and alkynes at room temperature with short reaction times.     

A Comparative Study of the Modification of Gold and Glassy Carbon Surfaces with Mixed Layers of In Situ Generated Aryl Diazonium Compounds

In situ generated aryl diazonium cations were synthesized in the electrochemical cell by reaction of the corresponding amines with NaNO₂ in aqueous HCl. This paper reports a study of the formation of mixed layers from in situ generated aryl diazonium cations. Firstly, glassy carbon (GC) and gold electrode surfaces were modified with five single in situ generated aryl diazonium salts to obtain their corresponding reductive potential followed by the modification of GC and gold surfaces with eight binary mixed layers of in situ generated aryl diazonium salts. The difference between GC and gold surfaces in terms of in situ formation of two‐component aryl diazonium salt films was compared. The behavior of the mixed layers formed from in situ generated aryl diazonium salts relative to diazonium salts that were pre‐synthesized prior to surface modification was also investigated. Cyclic voltammetry and X‐ray photoelectron spectroscopy were used to characterize the resulting modified GC and gold surfaces. It is found that for some aryl diazonium salts the potential at which reductive adsorption is achieved on gold and GC surfaces is significantly different. For the eight sets of binary mixed layers, the species with more anodic potential are more difficult to attach to the both GC and gold surfaces. The behavior of the mixed layers formed from in situ generated aryl diazonium salts and the pre‐synthesized diazonium salts is similar; which emphasizes the advantage of the in situ approach without any apparent difference in behavior to the presynthesized diazonium salts.     

Spontaneous grafting of diazonium salts: chemical mechanism on metallic surfaces

The spontaneous reaction of diazonium salts on various substrates has been widely employed since it consists of a simple immersion of the substrate in the diazonium salt solution. As electrochemical processes involving the same diazonium salts, the spontaneous grafting is assumed to give covalently poly(phenylene)-like bonded films. Resistance to solvents and to ultrasonication is commonly accepted as indirect proof of the existence of a covalent bond. However, the most relevant attempts to demonstrate a metal-C interface bond have been obtained by an XPS investigation of spontaneously grafted films on copper. Similarly, our experiments give evidence of such a bond in spontaneously grafted films on nickel substrates in acetonitrile. In the case of gold substrates, the formation of a spontaneous film was unexpected but reported in the literature in parallel to our observations. Even if no interfacial bond was observed, formation of the films was explained by grafting of aryl cations or radicals on the surface arising from dediazoniation, the film growing later by azo coupling, radical addition, or cationic addition on the grafted phenyl layer. Nevertheless, none of these mechanisms fits our experimental results showing the presence of an Au-N bond. In this work, we present a fine spectroscopic analysis of the coatings obtained on gold and nickel substrates that allow us to propose a chemical structure of such films, in particular, their interface with the substrates. After testing the most probable mechanisms, we have concluded in favor of the involvement of two complementary mechanisms which are the direct reaction of diazonium salts with the gold surface that accounts for the observed Au-N interfacial bonds as well as the formation of aryl cations able to graft on the substrate through Au-C linkages.     

The decomposition of aryl diazonium borofluorides in nitrobenzene and ethyl benzoate in the presence of the free metal,copper powder

Summary In the presence of copper powder the decomposition of aryl diazonium borofluorides in nitrobenzene and ethyl benzoate gives products of homolytic splitting of the diazonium salts. The synthesis of metalloorganic compounds from diazonium salts in the presence of metals occurs by a homolytic mechanism.     

Waste-free chemistry of diazonium salts and benign separation of coupling products in solid salt reactions

Gas-solid and solid-solid techniques allow for waste-free and quantitative syntheses in the chemistry of diazonium salts. Five techniques for diazotations with the reactive gases NO(2), NO and NOCl are studied. Two types are mechanistically investigated with atomic force microscopy (AFM) and are interpreted on the basis of known crystal packings. The same principles apply to the cascade reactions that had been derived from one-step reactions. Solid diazonium salts couple quantitatively with solid diphenylamine and anilines to give the triazenes. Azo couplings are achieved with quantitative yields by cautious co-grinding of solid diazonium salts with beta-naphthol and C-H acidic heterocycles, such as barbituric acids or pyrazolinones. Solid diazonium salts may be more easily applied in a stoichiometric ratio for couplings in solution. Co-grinding of solid diazonium salts with KI gives quantitative yields of various solid aryl iodides. The unavoidable coupling products in salt reactions are completely separated from the insoluble products in a highly benign manner. The solid-state reactions compare favourably with similar solution reactions that produce much waste. The structures of the products are elucidated with IR and NMR spectroscopy and mass spectrometry, while the tautomeric properties of the compounds are studied with density functional calculations at the B3LYP/6-31G* and BLYP/6-31G** levels.     

Copper‐Promoted Sandmeyer Difluoromethylthiolation of Aryl and Heteroaryl Diazonium Salts

An efficient copper‐promoted difluoromethylthiolation of aryl and heteroaryl diazonium salts is described. The reaction is conducted under mild reaction conditions and various functional groups were compatible. In addition, reactions of heteroaryl diazonium salts such as pyridyl, quinolinyl, benzothiazolyl, thiophenyl, carbazolyl, and pyrazolyl diazonium salts occurred smoothly to afford the medicinally important difluoromethylthiolated heteroarenes. Furthermore, a more practical one‐pot direct diazotization and difluoromethylthiolation protocol was developed, and it converts the aniline derivatives into difluoromethylthiolated arenes. The utility of the method is demonstrated by difluoromethylthiolation of a number of natural products and drug molecules.     

Allylation and vinylation of aryl radicals generated from diazonium salts

Allylation and vinylation of aryl radicals generated from aryl diazonium salts provides rapid and efficient access to chlorinated and brominated derivatives of styrene and allylbenzene. Allyl chlorides were found to be better substrates than bromides due to decreased halogen transfer. Donor- and acceptor-substituted diazonium salts are well tolerated. The products represent important precursors for numerous further transformations.     

The fabrication of stable gold nanoparticle-modified interfaces for electrochemistry

Forming stable gold nanoparticle (AuNP)-modified surface is important for a number of applications including sensing and electrocatalysis. Herein, tethering AuNPs to glassy carbon (GC) surfaces using surface bound diazonium salts is investigated as a strategy to produce stable AuNP surfaces. GC electrodes are first modified with 4-aminophenyl (GC-Ph-NH(2)), and then the terminal amine groups are converted to diazonium groups by incubating the GC-Ph-NH(2) interface in NaNO(2) and HCl solution to form a 4-phenyl diazonium chloride-modified interface (GC-Ph-N(2)(+)Cl(-)). Subsequently AuNPs are immobilized on the interface by electrochemical reduction to give a 4-phenyl AuNP-modified interface (GC-Ph-AuNP). For comparison, 4-aminophenyl AuNP- and 4-thiophenol AuNP-modified GC interfaces (GC-Ph-S-AuNP and GC-Ph-NH-AuNP), in which AuNPs are tethered to the surfaces by forming S-Au and NH-Au bond, respectively, were also prepared. Cyclic voltammetry, electrochemical impedance spectroscopy, X-ray photoelectron spectroscopy, and scanning electron microscopy are used to characterize these fabricated interfaces. The AuNP on GC-Ph-AuNP surfaces demonstrate good stability under sonication in Milli-Q water, during electrochemical treatment in 0.05 M H(2)SO(4) solution, and over several weeks. By contrast, the GC-Ph-NH-AuNP and GC-Ph-S-AuNP surfaces showed significant particle losses under equivalent conditions.     

硫杂蒽酮光敏分解重氮盐及其用作光引发体系的研究

本工作对几种新型硫杂蒽酮化合物敏化光解重氮盐问题进行了研究。工作表明:敏化反应是通过电子转移过程实现的,重氮盐所带取代基以及溶剂对重氮盐的光解有较大影响。十分有趣的是该体系对甲基丙烯酸甲酯进行光敏自由基引发聚合的速率和其光解反应速率有很大的不同,本文对此现象进行了讨论。     

几种芳香萘环重氮盐热解性质的研究

重氮盐是日益广范应用的光敏和热敏材料。国内外学者对重氮盐热解稳定性等问题的研究早有报道.前人研究认为:重氮盐热分解时发生C—N键的断裂,分为异裂和均裂两种.在酸性水溶液中为异裂反应,生成芳烃正离子;在碱性水溶液或醇溶液中,大多发生均裂反应,生成游离基.Brown及角田等研究发现:在苯环重氮基对位上引入强正极性基能增加重氮盐的热稳定性,但Crossley等人发现,在重氮基对位上的取代基,无论是吸电子的硝基(-NO_2)或是给电子的甲氧基(-OCH_3),都能增加重氮盐的热稳定性.然而人们还未能从理论上对于上述问题予以深入明确的探讨.取代基的不同、热解产物的不同以及     

取代苯基重氮盐的直接光解和敏化光解的研究

本工作合成了一系列带取代基的苯基重氨盐化合物。对它们的直接光解研究表明:带推电子基的重氮盐化合物具有较高的光解反应速度,但在敏化光解研究中发现:带有拉电子基的重氟盐化合物,不论是它的敏化光解或是猝灭敏化剂荧光的能力都较带推电子基的重氮盐为强,这清晰地表明,此敏化过程是通过电子转移反应而实现的。工作中还发现,在基态条件下,重氮盐和N,N-二甲基苯胺间可生成电荷转移络合物(CTC),经Benesi-Hildebrand公式处理表明:可形成1:1的CTC。     

The Electrochemical Grafting of a Mixture of Substituted Phenyl Groups at a Glassy Carbon Electrode Surface

Two‐component substituted aryl groups are simultaneously grafted onto the surface of a glassy carbon electrode by electrochemical reduction of a binary mixture of two aryl diazonium salts in acetonitrile. The electrochemical deposition is achieved potentiostatically and two different mixtures with four different ratios of diazonium salts are used. The binary mixtures comprise: 1) 4‐nitrophenyl diazonium and 4‐bromophenyl diazonium cations and 2) 4‐bromophenyl diazonium and N,N‐diethylaniline diazonium cations. The chemical composition of the two component films is determined by cyclic voltammetry in an electrolyte inert for electroactive groups such as nitrophenyl and bromophenyl. X‐ray photoelectron spectroscopy is also used to evaluate the surface concentration of each grafted substituted phenyl group. The surface concentration of the substituted phenyl group for which the corresponding diazonium cation is the most easily reduced is higher than its concentration in the mixture of the deposition solution. The usefulness of binary films is also discussed.     

Reactivity of diazoazoles and azolediazonium salts in <Emphasis Type="Italic">C</Emphasis>-azo coupling reactions

The comparative reactivity of heterocyclic diazo compounds and the corresponding diazonium salts in C-azo coupling reactions was studied using imidazole, pyrazole, and triazole derivatives as examples.The reactivities of pyrazole- and imidazole-derived diazonium salts are much lower than those of thiadiazole- and 1,2,4-triazole-derived diazonium salts but higher than those of pyrrole and indole diazo compounds.__________Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 2, pp. 348–358, February, 2005.     

Hydrolysis of Diazonium Salts Using a Two‐Phase System (CPME and Water)

A new method for the hydrolysis of diazonium salts, without the formation of tar, was developed. A two‐phase system consisting of cyclopentyl methyl ether (CPME) and water is very effective for the hydrolysis of diazonium salts. Using this solvent system, the diazonium salt prepared from 3‐(4‐nitrophenoxy)aniline gave 3‐(4‐nitrophenoxy)phenol in high yield (96%) within 20 min. The synthesized phenol is an industrially important raw material in polymer syntheses. Furthermore, the use of the present two‐phase system of CPME and water successfully brought about the efficient conversions of several m‐substituted anilines into the corresponding m‐substituted phenols. This is the first example of hydrolysis of diazonium salts using the two‐phase system (CPME and water).     

Time-of-flight secondary ion mass spectroscopy characterization of the covalent bonding between a carbon surface and aryl groups

Grafting of aryl layers derived from aryl diazonium salts onto glassy carbon electrodes is observed by time-of-flight secondary ion mass spectroscopy (ToF-SIMS). The grafting occurs spontaneously when a glassy carbon plate is immersed into a solution of aryl diazonium salt and can be enhanced by biasing the carbon plate at a potential a little more negative than the diazonium salt reduction. C-C and C-O covalent bonding are believed to be responsible for the strong attachment of these layers onto the carbon substrate. Fragments containing aryl dimers, trimers, or tetramers are also observed. A mechanism is proposed to account for the formation of these polymeric chains.     

Researches on synthetic dyes

It is shown that formazan-type compounds can be synthesized by coupling diazonium salts with nitrogen containing N-aryllepidine salts. N-phenyllepidinium perchlorate is used to prepare 8 dyes of the type mentioned.For Part LV see [6]     

Three component reaction of aryl diazonium salt with sulfonamide & actonitrile to synthesize N-sulfonyl amidine

A new method was developed to prepare N-sulfonyl amidine compounds through three-component reaction of aryl diazonium salts with sulfonamides and acetonitrile, in which, nitrilium ion intermediate, generated from the reaction of aryldiazonium salt with nitrile, was subsequently trapped by sulfonamides. A series of N-sulfonyl amidine derivatives were synthesized by using various types of aryl diazonium salts, sulfonamides and nitriles. In addition, indolyl imine products could also be prepared by using indole as the nucleophile to trap nitrilium ion intermediate.     

Metal-free, visible-light-mediated direct C-H arylation of heteroarenes with aryl diazonium salts

Visible light along with 1 mol % eosin Y catalyzes the direct C-H bond arylation of heteroarenes with aryl diazonium salts by a photoredox process. We have investigated the scope of the reaction for several aryl diazonium salts and heteroarenes. The general and easy procedure provides a transition-metal-free alternative for the formation of aryl-heteroaryl bonds.     

Cathodic reduction of diazonium salts in aprotic medium

Cathodic reduction of diazonium salts in acetonitrile led to the formation of azobenzenes, in good to moderate yields, and diarylamines as minoritary products. The reactions were carried out at the second reduction potential of the diazonium salts, involving aryl anions in the formation of the products.