Thianthrene Cation Radical Research Articles

Reaction of Thianthrene Cation Radical with Diarylmercurials. Search for Single Electron Transfer Is Elusive

Diarylmercurials (Ar2Hg) with Ar = p-tolyl Ib, o-tolyl Ic, p-anisyl Id and 2-allyloxy-4,5-dimethylphenyl Ie, reacted with thianthrene cation radical perchlorate (Th.+ClO4-) in two stoichiometric ratios: 2 : 1 and 4 : 1 (Th.+ClO4-/Ar2Hg). In the 2 : 1 ratio the products were the 5-arylthianthreniumyl perchlorates IIb - IIe, thianthrene (Th) and ArHg+ClO4- (assayed as ArHgCl, III) in quantitative yields. In the 4 : 1 ratio reaction with ArHg+ occurred, too, and the products were IIb - IIe, Th, the complex Th3Hg(ClO4)2 and HgO (after workup). In contrast, Ph2Hg (Ia) did not react beyond the 2 : 1 stoichiometry. In the reactions with Ie, no evidence for formation and cyclization of free 2-allyloxy-4,5-dimethylphenyl radical was found. Reaction of and product formation from these arylmercurials, therefore, does not occur in single electron transfer steps that lead to free aryl radicals. Instead electron transfer appears to occur within a complex of Ar2Hg with Th.+ from which II and other products are subsequently formed.

Photoinduced electron transfer for high potential quinone sensitizers and thienthrenes. The rate of trapping of the thianthrene radical cation by water

Electron transfer properties of chlorinated benzoquinone triplet states are reported, including transient spectra and rates of electron transfer quenching by donor thianthrenes; a rate constant for the trapping of thianthene radical by water has been measured.

Reaction of thianthrene cation radical with alcohols: Cyclohexanols

Cyclohexanol ( 1), 4-methylcyclohexanol ( 2), 4- tert -butylcyclohexanol ( 3), cis -2-methyl- ( 4) and trans -2-methylcyclohexanol ( 5) reacted cleanly with thianthrene cation radical perchlorate (Th .+ClO 4 −) in the presence of 2,6-di- tert -butyl-4-methylpyridine (DTBMP). The alcohols were converted quantitatively into cyclohexenes, while Th .+ was converted quantitatively into thianthrene (Th) and thianthrene 5-oxide (ThO). The oxygen atom of ThO came from the alcohol, as was demonstrated with the use of [ 18O]cyclohexanol.

Reactions of phenols with thianthrene cation radical

The phenols 2-R 1 -6-R 2 -phenol 1a-g in which R 1 =R 2 =tert-butyl, methyl, isopropyl, Cl, Br, F, and H reacted with thianthrene cation radical perchlorate (Th .+ ClO 4 - ) to give 5-(4-hydroxyaryl)thianthreniumyl perchlorates 2a-g in good yield. o-Allylphenol (1i) behaved similarly. o-tert-Butylphenol (1h) gave both 5-(3-tert-butyl-4- hydroxyphenyl)thianthreniumyl perchlorate (2h) and a quinonoidal perchlorate (3), namely, 5-(3- thianthreniumyl-5-tert-butyl-6-oxo-2,4-cyclohexadien-1-ylidene)-5,5- dihydrothianthrene perchlorate

Isotopically selective electron transfer between free radical cations and their parent molecules enables isotope enrichment

Electron transfer between the thianthrene radical cation and its neutral molecule precursor shows a significant H/D equilibrium isotope effect which may be used for isotopic enrichment.

Oxidation of organotins (R4Sn, RSnMe3, and R3SnSnR3) by the thianthrene cation radical

Reactions of thianthrene cation radical perchlorate (Th •+ ClO 4 − ) with R 4 Sn, R=methyl(Me), ethyl(Et), n-butyl(Bu), phenyl(Ph), and vinyl, in acetonitrile took place cleanly in the stoichiometric ratio Th •+ ClO 4 − /R 4 Sn 2:1. Oxidative cleavage of R 4 Sn occurred into R 3 Sn 3+ , that was assayed as R 3 SnCl, and the radical R • . The latter was primarily trapped as the 5-R-thianthreniumyl perchlorate, although abstraction of hydrogen atom from the solvent was significant in the cases of phenyl and vinyl radicals. Reactions of Th •+ ClO 4 − with RSnMe 3 , R=allyl, vinyl, Ph, Et, isopropyl (i-Pr), and tert-butyl (t-Bu), occurred with the same stoichiometry. Exclusive loss of the i-Pr, t-Bu, and allyl groups occurred. From reaction of Th •+ ClO 4 − with R 6 Sn 2 (R=Me and Ph) R 3 Sn + was formed exclusively; that is, the R 2 Sn 2 underwent two-electron oxidation

Reactions of thianthrene cation radical with oximes of cinnamaldehydes and unsaturated aromatic ketones in acetonitrile

Reactions of thianthrene cation radical with oximes of cinnamaldehydes and unsaturated aromatic ketones in acetonitrile

ChemInform Abstract: Reactions of Oximes with Thianthrene Cation Radical in Nitrile Solvents. Cycloaddition to Form Oxadiazoles and Deoxygenation to Form Nitriles.

AbstractReaction of the aldoximes (I) with the thianthrene radical cation perchlorate (II) yields the parent aldehydes (IV), the corresponding nitriles (V), and in some case the oxadiazoles (VI) and (VII), formed by oxidative cycloaddition.

Evidence for electron transfer in reactions of thianthrene cation radical with dialkylmercurials [Erratum to document cited in CA112(21):198622b

Evidence for electron transfer in reactions of thianthrene cation radical with dialkylmercurials [Erratum to document cited in CA112(21):198622b

Reactions of oximes with thianthrene cation radical in nitrile solvents. Cycloaddition to form oxadiazoles and deoxygenation to form nitriles

Reactions of eight oximes, RCH=NOH (1a, R=C 6 H 5 ; 1b, R=4-CH 3 C 6 H 4 ; 1c, R=4-NO 2 C 6 H 4 ; 1d, R=4-CH 3 OC 6 H 4 ; 1e, R=2-CH 3 OC 6 H 4 ; 1f, R=1-naphthyl; 1g, R=C 5 H 11 ; 1h, R=C 4 H 9 ) with thianthrene cation radical perchlorate (Th •+ ClO 4 − ) in acetonitrile under argon were studied. The major product from the oxime in all cases, but of 1d, was the nitrile, RCN

Evidence for electron transfer in reactions of thianthrene cation radical with dialkylmercurials

Reactions of dialkylmercurials (R 2 Hg) with thianthrene cation radical perchlorate (Th •+ ClO 4 − ) in acetonitrile solution have been studied in quantitative detail. Evidence was obtained from reactions of MeHgR (R=Et, i-Pr, t-Bu) that reaction begins with electron transfer rather than with electrophilic cleavage of an alkyl-mercury bond

ChemInform Abstract: Reactions of Phenylmagnesium Chloride and Phenyllithium with Thianthrene Cation Radical Perchlorate. Evidence for Electron Transfer: Formation and Decomposition of 5‐Substituted Thianthreniumyl Perchlorates.

AbstractReaction of the radical cation perchlorate (I) with phenylmagnesium chloride (II) gives mainly benzene (III), thianthrene (IV), and ‐ via electron transfer ‐ 5‐phenylthianthrene (Vc).

Reactions of phenylmagnesium chloride and phenyllithium with thianthrene cation radical perchlorate. Evidence for electron transfer: formation and decomposition of 5-substituted thianthreniumyl perchlorates

ADVERTISEMENT RETURN TO ISSUEPREVArticleNEXTReactions of phenylmagnesium chloride and phenyllithium with thianthrene cation radical perchlorate. Evidence for electron transfer: formation and decomposition of 5-substituted thianthreniumyl perchloratesBogdan Boduszek, Henry J. Shine, and T. Krishnan VenkatachalamCite this: J. Org. Chem. 1989, 54, 7, 1616–1626Publication Date (Print):March 1, 1989Publication History Published online1 May 2002Published inissue 1 March 1989https://doi.org/10.1021/jo00268a024RIGHTS & PERMISSIONSArticle Views650Altmetric-Citations13LEARN ABOUT THESE METRICSArticle Views are the COUNTER-compliant sum of full text article downloads since November 2008 (both PDF and HTML) across all institutions and individuals. These metrics are regularly updated to reflect usage leading up to the last few days.Citations are the number of other articles citing this article, calculated by Crossref and updated daily. Find more information about Crossref citation counts.The Altmetric Attention Score is a quantitative measure of the attention that a research article has received online. Clicking on the donut icon will load a page at altmetric.com with additional details about the score and the social media presence for the given article. Find more information on the Altmetric Attention Score and how the score is calculated. Share Add toView InAdd Full Text with ReferenceAdd Description ExportRISCitationCitation and abstractCitation and referencesMore Options Share onFacebookTwitterWechatLinked InReddit PDF (1 MB) Get e-Alerts Get e-Alerts

ChemInform Abstract: Formation of 1,2,4‐Triazoles by Cation Radical Induced Oxidative Addition of Arylhydrazones of Benzaldehyde and Butyraldehyde to Nitriles.

AbstractThe aldehyde hydrazones (II) are oxidized with a thianthrene cation radical to form nitrilimines which undergo in situ 1,3‐dipolar cycloaddition reaction with the nitrile (I), producing the 1,2,4‐triazoles (III).

Resonance Raman Spectroscopic Studies of Electrogenerated Cation Radicals by Column-Electrolytic Continuous-Flow Method

Abstract For the measurement of resonance Raman (RR) spectra of electrogenerated cation radicals in solution, a column-electrolytic continuous-flow method has been developed. This method has the advantage that the concentration of cation radicals can be easily varied by controlling the applied current. The RR spectra of the thianthrene cation radical (TH+·) have been successfully observed. The structure of TH+· is discussed, based on the assignment of the RR band. The RR spectra of the oxidized solutions of three aromatic amines have also been measured. These spectra were assigned not due to those of cation radicals but to those of dimer cation radicals produced in the consecutive reactions.

Preparation of solid thianthrene cation radical tetrafluoroborate

Preparation of solid thianthrene cation radical tetrafluoroborate

ChemInform Abstract: Oxidative Cyclization of Arylhydrazones of Chalcones and Benzalacetones to Pyrazoles by Thianthrene Cation Radical.

ChemInformVolume 19, Issue 37 Heterocyclic Compounds ChemInform Abstract: Oxidative Cyclization of Arylhydrazones of Chalcones and Benzalacetones to Pyrazoles by Thianthrene Cation Radical. A. C. KOVELESKY, A. C. KOVELESKY Dep. Chem. Biochem., Tex. Tech. Univ., Lubbock, TX 79409, USASearch for more papers by this authorH. J. SHINE, H. J. SHINE Dep. Chem. Biochem., Tex. Tech. Univ., Lubbock, TX 79409, USASearch for more papers by this author A. C. KOVELESKY, A. C. KOVELESKY Dep. Chem. Biochem., Tex. Tech. Univ., Lubbock, TX 79409, USASearch for more papers by this authorH. J. SHINE, H. J. SHINE Dep. Chem. Biochem., Tex. Tech. Univ., Lubbock, TX 79409, USASearch for more papers by this author First published: September 13, 1988 https://doi.org/10.1002/chin.198837205Read 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. Volume19, Issue37September 13, 1988 RelatedInformation

Oxidative cyclization of arylhydrazones of chalcones and benzalacetones to pyrazoles by thianthrene cation radical

Oxidative cyclization of arylhydrazones of chalcones and benzalacetones to pyrazoles by thianthrene cation radical

ChemInform Abstract: Reaction of Thianthrene Cation Radical with Grignard Reagents. Evidence for Electron Transfer and Trapping of Alkyl Radicals by the Thianthrene Cation Radical.

Abstract Reactions are reported between RMgCl and thianthrene cation radical perchlorate (Th .+ ClO - 4 ) suspended in ether and tetrahydrofuran (THF). In ether solution reactions R = Bu, s-Bu, t-Bu, 5-hexenyl, and cyclopentylmethyl. Major products were the alkane, the alkene R(-H) in some cases, and, in the cases of R = Bu, 5-hexenyl, and cyclopentylmethyl, the 5-alkylthianthrenium perchlorate (ThR + ClO - 4 ). When 5-hexenylMgCl was used a mixture of 5-(5-hexenyl)- and 5-(cyclopentylmethyl)thianthrenium per-chlorates in the ratio of approximately 2 was obtained. Since the ratio of 5-hexenyl/cyclopentylmethyl in the Grignard reagent was 10.4, it is concluded that the C 6 sulfonium ions were formed by radical trapping by Th .+ after single electron transfer from Grignard to cation radical had occurred, thus allowing for cyclization of 5-hexenyl radical. Formation of ThBu + ClO - 4 is attributed to the trapping of butyl radical by Th ·+ , while formation of RH and R(-H) is in all cases also attributed to alkyl radical reactions. Reactions in THF(R = Me, i-Pr, Bu, s-Bu, t-Bu, Ph) led almost exclusively to RH and Th. Polymerization of THF was also initiated and took place slowly giving rise to low molecular weight poly(THF). By using THF- d 8 , as solvent for reaction between BuMgCl and Th .+ , it was possible to find Bu groups ( 1 H-NMR) in the poly(THF- d 8 ). Polymerization of THF is attributed, in some cases (R = Me, Bu), to alkyl-cation transfer from ThR + to THF. In other cases initiation of polymerization by R + and THF(-H) + is considered.

Reaction of thianthrene cation radical with grignard reagents : Evidence for electron transfer and trapping of alkyl radicals by the thianthrene cation radical

Reactions are reported between RMgCl and thianthrene cation radical perchlorate (Th .+ClO - 4) suspended in ether and tetrahydrofuran (THF). In ether solution reactions R = Bu, s-Bu, t-Bu, 5-hexenyl, and cyclopentylmethyl. Major products were the alkane, the alkene R(-H) in some cases, and, in the cases of R = Bu, 5-hexenyl, and cyclopentylmethyl, the 5-alkylthianthrenium perchlorate (ThR +ClO - 4). When 5-hexenylMgCl was used a mixture of 5-(5-hexenyl)- and 5-(cyclopentylmethyl)thianthrenium per-chlorates in the ratio of approximately 2 was obtained. Since the ratio of 5-hexenyl/cyclopentylmethyl in the Grignard reagent was 10.4, it is concluded that the C 6 sulfonium ions were formed by radical trapping by Th .+ after single electron transfer from Grignard to cation radical had occurred, thus allowing for cyclization of 5-hexenyl radical. Formation of ThBu +ClO - 4 is attributed to the trapping of butyl radical by Th ·+, while formation of RH and R(-H) is in all cases also attributed to alkyl radical reactions. Reactions in THF(R = Me, i-Pr, Bu, s-Bu, t-Bu, Ph) led almost exclusively to RH and Th. Polymerization of THF was also initiated and took place slowly giving rise to low molecular weight poly(THF). By using THF- d 8, as solvent for reaction between BuMgCl and Th .+, it was possible to find Bu groups ( 1H-NMR) in the poly(THF- d 8). Polymerization of THF is attributed, in some cases (R = Me, Bu), to alkyl-cation transfer from ThR + to THF. In other cases initiation of polymerization by R + and THF(-H) + is considered.