Reactions Of Arenediazonium Salts Research Articles

Desulfinylative Pd-catalyzed coupling reaction of arenediazonium salt with aryl sulfinates to give unsymmetrical biaryls

Abstract An efficient route for the synthesis of unsymmetrical biaryls was developed via palladium catalyzed reaction of arenediazonium salts and aryl sulfinates under inert atmosphere. This synthesis involves cascade processes. Tetrabutylammonium iodide was used as an iodide source for in situ formation of aryl iodide, followed by desulfinylative cross-coupling reaction between aryl sulfinates and aryl iodides. A wide range of biaryls were selectively prepared in one pot from simple substrates in good to excellent yields.

ChemInform Abstract: An Efficient Route to 1,3,5‐Triazido‐2,4,6‐tricyanobenzene.

Benzonitriles and organic azides are of particular importance as components of dyes, herbicides, natural products, and drugs [1 – 6]. For example, it is possible to convert the nitrile group into a variety of other functional groups. Therefore benzonitriles are important intermediates for the synthesis of biologically important structures such as benzoic acid derivatives, benzyl amines, benzyl amides, and heterocyclic compounds. Due to the diverse applications of benzonitrile numerous synthetic possibilities have been developed. In particular, the Rosenmund-von-Braun reaction [7] (reaction of aryl halides with copper(I) cyanide) and the Sandmeyer reaction [8] (reaction of arene-diazonium salts with copper(I) cyanide) are used. The problem of both methods is the formation of stoichiometric amounts of heavy metal salts. Therefore, today aryl cyanides are produced primarily by the ammoxidation of the corresponding toluenes [9, 10]. This process requires harsh reaction conditions and shows a lack of tolerance of other functional groups. Another way to generate the nitrile group is the stepwise construction of a CN moiety by application of a series of classical organic synthesis steps as shown in Scheme 1. Here we report on the stepwise synthesis and full characterization of binary 1,3,5-triazido-2,4,6tricyanobenzene. Results and Discussion

ChemInform Abstract: Preparation and NMR Analysis of 2,6-Heterodifunctional Halobenzenes as Precursors for Substituted Biphenyls.

Abstract Preparation and complete characterization of 16 2,6-disubstituted halobenzenes, including nine new compounds, from two common starting materials is described. Seven of the new compounds contain one or two propylthio groups, which have been introduced in two ways. Direct reaction of arenediazonium salts with 1-propanethiolate gives yields comparable to those obtained in a three-step method through sulfonyl chlorides. The 1 H- and 13 C NMR chemical shifts of 17 1,2,3-trisubstituted benzenes have been correlated with the predicted values and the observed trends explained using commonly available modeling packages.

Recoverable Homogeneous Palladium(0) Catalyst for Cross‐Coupling Reactions of Arenediazonium Salts with Potassium Organotrifluoroborates: Detection of Catalytic Intermediates by Electrospray Ionization Mass Spectrometry

AbstractFifteen‐membered triolefinic macrocyclic palladium(0) complex 1, (E,E,E)‐1‐ferrocenylsulfonyl‐6,11‐bis[(4‐methylphenyl)sulfonyl]‐1,6,11‐triazacyclopentadeca‐3,8,13‐trienepalladium(0), is an active and recoverable catalyst for Suzuki–Miyaura cross‐couplings between arenediazonium salts and potassium organotrifluoroborates. The reactions were performed under aerobic conditions at room temperature and without added base. Use of electrospray ionization mass spectrometry (ESI‐MS) allowed the direct detection and identification of several intermediates, which furthers the study of the mechanistic aspects of the Suzuki–Miyaura reaction. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2007)

Reaction of Arenediazonium Salts and SO2 with α‐Nitroolefins.

AbstractFor Abstract see ChemInform Abstract in Full Text.

Probing the mechanism of the Heck reaction with arene diazonium salts by electrospray mass and tandem mass spectrometry.

Key ionic intermediates of the Heck reaction of arene diazonium salts have been intercepted and structurally characterized by ESI-MS/MS. The use of electrospray ionization enables the ionic species to be transferred smoothly to the gas phase. A catalytic cycle for this reaction involving all the Pd cationic species intercepted has been proposed (see scheme).

Synthetic Studies on Tetrastilbenylmethane Dendrimers: Preparation and Optical Properties of a Second Generation Dendron.

Towards synthesis of tetrastilbenylmethane dendrimers, a second generation tristilbenylmethylstyrene dendron has been prepared from the commercial dye stuff New Fuchsin. Heck reaction of arenediazonium salts with vinyl trimethylsilane is strategically used to construct the focal styrene unit of the dendron. Preliminary optical studies show strong absorption and emission properties for this dendron.

ChemInform Abstract: Reactions of Arenediazonium Salts with Tetrathiafulvalene and Related Electron Donors: A Study of “Radical‐Polar Crossover” Reactions

AbstractChemInform is a weekly Abstracting Service, delivering concise information at a glance that was extracted from about 100 leading journals. To access a ChemInform Abstract of an article which was published elsewhere, please select a “Full Text” option. The original article is trackable via the “References” option.

Reactions of Arenediazonium Salts with Diazadithiafulvalenes

The kinetics of coupling of carbon radicals with sulfur radical-cations in diazadithiafulvalenes is sensitive to the steric environment around sulfur. © 1997 Elsevier Science Ltd.

The effect of ortho and para substituents on the formation of the E and Z isomers of the arylhydrazones obtained from diazonium coupling with methyl 3-aminocrotonate and 3-aminocrotononitrile

Reaction of arene diazonium salts with 3-aminocrotononitrile or methyl 3-aminocrotonate affords the 2-aryl-hydrazono-3-oxobutanenitrile (1 or 3 and 3′) or the methyl 2-arylhydrazono-3-oxobutanoate (2 and 2′ or 4 and 4′). A series of these hydrazones has been prepared with a range of electron-withdrawing and -donating substituents in the ortho or para position of the aryl moiety. The hydrazones have been characterized by spectroscopic methods, with emphasis on the 1H NMR spectra, which have been used to determine the configuration of the hydrazones as E or Z or a mixture of the two. The para-substituted hydrazononitriles (1) are formed as a single species, namely the Z isomer, whereas the ortho isomers are formed as a mixture of E and Z configurations (3 and 3′). The hydrazonobutanoates (2 and 2′ or 4 and 4′) are formed as E/Z mixtures regardless of the position of the substituent in the aryl moiety. Complete assignments of all signals in the 1H NMR spectra have been made on the basis of the ability of the various substituents to participate in intramolecular hydrogen bonding and a mechanism is proposed to account for the variations in the proportions of E and Z isomers and the effect of the nature of the substituent on this ratio. 13C NMR spectra of selected hydrazones have been recorded as an aid to structure assignment. Key words: hydrazone, diazonium, NMR spectroscopy, E/Z isomers, crotonic acid derivatives.

Reaction of Arenediazonium Salts with Nitriles in the Presence of Sodium Carboxylates. A Convenient Synthesis of Unsymmetrical N-Aryl Acyclic Imides

Abstract Reactions of arenediazonium tetrafluoroborates (ArN2BF4), acetonitrile and sodium carboxylates (RCOONa) gave N-acyl acetanilides (ArN(COR)COCH3) in moderate to good yields (Ar=Ph, 2-MeC6H4, 3-MeC6H4, 4-MeC6H4, 2,6-(Me)2C6H3; R=Et, i-Pr, t-Bu, Ph). Acrylonitrile and benzonitrile could be used in the reaction instead of acetonitrile.

Electron Transfer Free Radical Mechanism in the Reaction of Arenediazonium Salts with Grignard Reagents

Electron Transfer Free Radical Mechanism in the Reaction of Arenediazonium Salts with Grignard Reagents

Synthesis of Aryliodides from Diazonium Tetrafluoroborate in Dimethylsulfoxide

Abstract One of the best methods for the introduction of iodine in the aromatic ring, is the reaction of arenediazonium salts with iodine ions in water1, for which a free radical mechanism was proposed2. Although the yields are generally good, numerous attempts were made to improve the method and to simplify the isolation procedure.

ChemInform Abstract: SUBSTITUENT EFFECTS IN THE REACTION OF ARENEDIAZONIUM SALTS WITH METHYLAMINE

Chemischer InformationsdienstVolume 5, Issue 2 Isocyclic Compounds ChemInform Abstract: SUBSTITUENT EFFECTS IN THE REACTION OF ARENEDIAZONIUM SALTS WITH METHYLAMINE T. P. AHERN, T. P. AHERNSearch for more papers by this authorK. VAUGHAN, K. VAUGHANSearch for more papers by this author T. P. AHERN, T. P. AHERNSearch for more papers by this authorK. VAUGHAN, K. VAUGHANSearch for more papers by this author First published: January 15, 1974 https://doi.org/10.1002/chin.197402177Read the full textAboutPDF ToolsRequest permissionExport citationAdd to favoritesTrack citation ShareShare Give accessShare full text accessShare full-text accessPlease review our Terms and Conditions of Use and check box below to share full-text version of article.I have read and accept the Wiley Online Library Terms and Conditions of UseShareable LinkUse the link below to share a full-text version of this article with your friends and colleagues. Learn more.Copy URL Share a linkShare onFacebookTwitterLinked InRedditWechat No abstract is available for this article. Volume5, Issue2January 15, 1974 RelatedInformation

Reaction of arenediazonium salts with rhodanine, thiohydantoin, and their derivatives

Under conditions of the O,S-arylation of rhodanine and isorhodanine by arenediazonium salts, 5-arylhydrazono-2-arylthio-2-thiazolin-4-ones and 5-arylhydrazono-4-arylthio-3-thiazolin-2-ones have been obtained. Under similar conditions, 5-ethylrhodanine forms not only 2-arylthio-5-ethyl-2-thiazolin-4-ones but also 2-arylazothio-5-ethyl-2-thiazolin-4-ones.