76874-24-3

Upstream product

• 15546-43-7 N,N,N',N'-tetraphenyl-4,4'-diaminobiphenyl 
• 603-34-9 2,4,6-tri-tert-butylanilino radical 
• 603-34-9 N,N-diphenylaminobenzene 

Relevant academic research and scientific papers

Identification of Fleeting Electrochemical Reaction Intermediates Using Desorption Electrospray Ionization Mass Spectrometry

We report a new method for the mass spectrometric detection of fleeting reaction intermediates in electrochemical reactions utilizing a "waterwheel" working electrode setup. This setup takes inspiration from desorption electrospray ionization (DESI) mass spectrometry, where the sampling time is on the order of milliseconds, to sample directly from the surface of a working electrode for mass spectrometric analysis. We present data that show the formation of a diimine intermediate of the electrochemical oxidation of uric acid that has a lifetime in solution of 23 ms as well as data that provide evidence for the formation of a similar diimine species from the electrooxidation of xanthine, which has not been previously observed.

Redox Kinetics of Metal Complexes in Non-aqueous Solutions. Part 13. The Ferriin Oxidation of Aprotic Donors in Acetonitrile: Relationships between Donor and Reducing Capabilities

The reactions of a variety of neutral donors (D) with ferriin in acetonitrile have been examined.The course of reaction and the products formed vary depending on the base strength and the structure of the donor, the two competing mechanisms discerned being (a) oxidation of D and (b) deprotonation of the residual water or the MeCN solutions initiating the reaction of hydroxide ions with ferriin.For the stability of ferriin solutions, there is a decrease in the order MeNO2 > MeCN > dmf > py > hmpa > Et3N which is the order of increasing donor numbers (DN).The very strong donors hmpa and Et3N (and all other aliphatic amines as well) are readily oxidized via charge transfer in an initially formed 1:1 complex Fe(phen)3D(3+) whose nature is discussed.In the case of Et3N, this complex dissociates spontaneously into ferroin and Et3N(+), the latter giving diethylvinylamine which polymerizes with release of diethylamine.For hmpa, charge transfer in Fe(phen)3(hmpa)(3+) needs base catalysis of a second hmpa molecule.The radical thus formed deprives hydrogen from acetonitrile forming succinonitrile.In contrast, Et3PO though being similar in basicity, is not oxidized.This comparison emphasizes the peculiar role of alkyl groups linked to nitrogen for the oxidation chemistry of organic substrates.Donors of donor numbers below that of hmpa are not oxidized noticeably but give rise to mechanism (b).The hydroxide formed displaces partly phen, a greenish precipitate separating identified as a novel high-molecular weight congener of tetrakis(phen)diaquo-μ-oxo-di-iron(III).The following stability order of radicals , derived from the donors, is suggested, dmf > hmpa > MeCN > R3N > dmso.Further, the ferriin oxidation of triphenylamine has been examined.

Oxidation von Triphenylamin in Acetonitril an rotierenden Scheibenelektroden

The standard potential for the oxidation of triphenylamine to the radical cation in acetonitrile containing 0.1 M lithium perchlorate is U0/= 601 mV vs. the silver electrode in 0.1 M silver nitrate, the standard rate constant ks= 3.1*10-2 cm s-1, and the transfer coefficient α=0.58.The radical cation dimerizes at a rate constant k2 =2.2(+/-0.2)*103M-1s-1 yielding the N,N,N',N',-tetraphenylbenzidinium dication.The dimerization is followed by a rapid deprotonization and a rapid homogeneous oxidation of the benzidine by the triphenylamine radical cationyielding the semiquinoneimine and the quinonediimine at the ratio 2:3.The rate constant for the synproportionation of the quinonediimine and the benzidine yielding the semiquinoneimine was determined at k2 =4.1*106M-1s-1.The semiquinoneimine reacts with 2,6-lutidine in a reaction with rate constant k2 =137 M-1s-1 and with other bases.The kinetic data result from electrochemical and spectrophotometric measurements at the rotating disc electrode with optically transparent ring and at the rotating ring-disc electrode.Spectra of the extinction coefficients were determined for stable and transient reaction products. - Keywords: Organic electrochemistry / Reaction kinetics / Rotating disc / Spectrophotochemistry