cas 92-85-3, Thianthrene | Articles data

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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 equilibrum isotope effect which may be used for isotopic enrichment.
Liu, Zhong-Li,Lu, Jian-Min,Chen, Pin,Wang, Xi-Lu,Wen, Xiao-Lin,et al.
p. 76 - 77
(1992)
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Electron Transfer Rates in Highly Exothermic Reactions on Semiconductor-Electrolyte Interfaces, and the Deuterium Isotope Effect
Highly exothermic electron transfer rates were measured by semiconductor electrochemical techniques.Experiments demonstrate that the decreases in the electron transfer rates with the exothermicity of the reactions in so-called abnormal regions are much more moderate than the classical predictions, and that this is probably due to the effects of intramolecular vibrations such as C-H stretching and/or bending.
Nakabayashi, Seiichiro,Itoh, Kiminori,Fujishima, Akira,Honda, Kenichi
p. 5301 - 5303
(1983)
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Regio- and Stereoselective Thianthrenation of Olefins To Access Versatile Alkenyl Electrophiles
Herein, we report a regioselective alkenyl electrophile synthesis from unactivated olefins that is based on a direct and regioselective C?H thianthrenation reaction. The selectivity is proposed to arise from an unusual inverse-electron-demand hetero-Diels–Alder reaction. The alkenyl sulfonium salts can serve as electrophiles in palladium- and ruthenium-catalyzed cross-coupling reactions to make alkenyl C?C, C?Cl, C?Br, and C?SCF3 bonds with stereoretention.
Berger, Florian,Chen, Junting,Li, Jiakun,Plutschack, Matthew B.,Ritter, Tobias
p. 5616 - 5620
(2020)
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CHEMISTRY ON BENZOPENTATHIEPIN. REACTIONS OF BENZOPENTATHIEPIN WITH AROMATIC COMPOUNDS IN THE PRESENCE OF LEWIS ACID
Benzopentathiepin (BPT) reacted with many aromatic compounds such as benzene, 1,4-dimethylbenzene, and naphthalene in the presence of Lewis acid to give various thianthrenes in moderate yields, BPT was found to serve as a 1,4-dication synthon.
Sato, Ryu,Onodera, Akira,Goto, Takehiko,Saito, Minoru
p. 2563 - 2566
(1988)
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Gilman,Swayampati
p. 2163
(1956)
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5-Arylthianthreniumyl Perchlorates as a Benzyne Precursor
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Kim, Kab Sig,Ha, Sung Min,Kim, Jong Yup,Kim, Kyongtae
p. 6483 - 6486
(1999)
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Synthesis of 1- and 2-substituted thianthrenes
Lithiation of thianthrene at C-1 allows the synthesis of various 1-substituted thianthrenes for example thianthren-1-ylboronic acid and 1-tributylstannylthianthrene, which undergo palladium-catalysed couplings with aryl halides. 2-Bromothianthrene provides an entry to 2-substituted thianthrenes via lithium-halogen exchange then reaction of 2-lithiothianthrene with electrophiles including formation of the 2-boronic acid and 2-tributylstannylthianthrene which were coupled to aryl halides.
Lovell, James M.,Joule, John A.
p. 2391 - 2395
(1996)
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Murata et al.
p. 573
(1968)
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2,3,8,9-Dibenzo-5,6-(substituted)benzo-1,4-dithio-7-azacyclonona-2,5,8- trienes. Synthesis and Mechanistic Study
5-(2-Acetamidoaryl)thianthreniumyl perchlorates reacted with potassium hydroxide in methanol at reflux giving 2,3,8,9-dibenzo-5,6-(substituted)benzo-1,4-dithio-7-azacyclonona-2,5,8-trienes 4 in 43 to 75% yields, whereas the reactions of the same compounds with sodium hydride in the absence or in the presence of dimethyl sulfate in refluxing tetrahydrofuran gave N-acetylated and N-methylated 4 in 68 to 96% and 27 to 56% yields, respectively. The mechanism of the formation of the products might be explained by a nucleophilic attack of amide ions 10, 12, and 14 at the ispo-position of the thianthrene ring. A sulfuranyl radical mechanism might be involved in these reactions.
Kim, Kyongtae,Kim, Man Nyoung
p. 1 - 12
(1997)
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Keats
p. 1592
(1937)
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Addition of Thianthrene Cation Radical to Cycloalkenes. An Unexpected Monoadduct
Whereas the addition of thianthrene cation radical perchlorate (Th?+ClO4-) to cyclohexene gives a bisadduct, namely, trans-1,2-bis(5-thianthreniumyl)cyclohexane diperchlorate (1), and additon to other alkenes and alkynes also gives trans-bisadducts, addition to cyclooctene gave only a cis-monoadduct, namely, 1,2-(5,10-thianthreniumdiyl)cyclooctane diperchlorate (2a). Similar monoadducts 2b-d were obtained from the addition of Th?+BF4-, Th?+SbF6-, and Th?+PF6- to cyclooctene. The structure of the monoadduct was deduced from its 1H and 13C NMR spectra, from the stoichiometry of its formation, and from the stoichiometry of its reaction with NaSPh, which gave equimolar amounts of cyclooctene, thianthrene, and diphenyl disulfide. The structure was confirmed with X-ray crystallography. Addition of Th?+ salts to cyclopentene and cycloheptene gave mixtures of mono- and bisadducts. The bisadduct of Th?+SbF6- to cyclopentene, separated from the small amount of monoadduct by crystallization, was shown with X-ray crystallography to have the trans configuration.
Lee, Wang Keun,Liu, Bo,Park, Chan Won,Shine, Henry J.,Guzman-Jimenez, Ilse Y.,Whitmire, Kenton H.
p. 9206 - 9210
(1999)
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Exploiting amphiphilicity: Facile metal free access to thianthrenes and related sulphur heterocycles
Benzodithioloimines are reacted with arynes or alkynes substituted with electron-withdrawing groups to afford the corresponding thianthrene or benzo[b][1,4]dithiine derivatives. The transformation takes place under mild reaction conditions without any transition metal. Furthermore, the reaction mode could be expanded to 2-thiocyanatopyrroles yielding pyrrolothiazoles.
Pawliczek, Martin,Garve, Lennart K.B.,Werz, Daniel B.
p. 9165 - 9168
(2015)
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Allylic Amination of Alkenes with Iminothianthrenes to Afford Alkyl Allylamines
Allylic C-H amination is currently accomplished with (sulfon)amides or carbamates. Here we show the first allylic amination that can directly afford alkyl allylamines, enabled by the reactivity of thianthrene-based nitrogen sources that can be prepared from primary amines in a single step.
Chen, Junting,Cheng, Qiang,Lin, Songyun,Ritter, Tobias
p. 17287 - 17293
(2020/11/02)

Organic compound, electronic device and electronic device (by machine translation)
The present application relates to an organic compound, and containing an electronic device containing the organic compound and an electronic device, containing the organic compound, wherein the organic compound, main body is shown as a large planar structure, in a steric space by introducing an electron rich arylamine or a heteroarylamine substituent, at 9 position of the fluorene or the silicon fluorenyl group such that the hole transport performance of the compound is excellent. (by machine translation)
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Paragraph 0225-0226

(2020/04/22)

Dechalcogenization of Aryl Dichalcogenides to Synthesize Aryl Chalcogenides via Copper Catalysis
An application for dechalcogenization of aryl dichalcogenides via copper catalysis to synthesize aryl chalcogenides is disclosed. This approach is highlighted by the practical conditions, broad substrate scope, and good functional group tolerance with several sensitive groups such as aldehyde, ketone, ester, amide, cyanide, alkene, nitro, and methylsulfonyl. Furthermore, the robustness of this methodology is depicted by the late-stage modification of estrone and synthesis of vortioxetine. Remarkably, synthesis of more challenging organic materials with large ring tension under milder conditions and synthesis of some halogen contained diaryl sulfides which could not be synthesized using metal-catalyzed coupling reactions of aryl halogen are successfully accomplished with this protocol.
Cao, Fei,Chen, Jinhong,Deng, Jiedan,Deng, Xuemei,Hou, Yongsheng,Shao, Xiangfeng,Shi, Tao,Wang, Yongqiang,Wang, Zhen,Wu, Lingxi,Yang, Jinru,Yang, Yuhang
p. 2707 - 2712
(2020/03/11)

Pd-Catalyzed Site-Selective Borylation of Simple Arenes via Thianthrenation?
Site-selective borylation of simple arenes was realized in one pot via an electrophilic thianthrenation/Pd-catalyzed borylation sequence. The key to achieve this operatically simple process is the use of Pd catalysis, which could tolerate the solvent and acidic conditions used in the thianthrenation step. This protocol features mild conditions, broad functional group tolerance, and simple manipulations, and is suitable for late-stage functionalization of a wide range of pharmaceuticals and complex bioactive molecules.
Chen, Xiao-Yue,Huang, Yu-Hao,Zhou, Jian,Wang, Peng
supporting information
p. 1269 - 1272
(2020/08/13)

Site-Selective Silylation of Arenes Mediated by Thianthrene S-Oxide
The thianthrene S-oxide (TTSO)-mediated site-selective silylation of arenes has been realized via a thianthrenation/Pd-catalyzed silylation sequence. This method features a broad substrate scope and wide functional group tolerance under mild conditions and allows the synthesis of a set of (hetero)arylsilanes with operationally simple manipulations. The application and generality of the approach were further demonstrated by the late-stage functionalization of marketed drugs. This reaction also represents the first example of a Pd-catalyzed silylation reaction of aryl sulfonium salts.
Wu, Yichen,Huang, Yu-Hao,Chen, Xiao-Yue,Wang, Peng
supporting information
p. 6657 - 6661
(2020/09/02)

A Pd-catalyzed optional approach for the synthesis of dibenzothiophenes
A direct and practical approach for the construction of DBTs was developed via a Pd-catalyzed tandem reaction, in which commercially available o-bromo-iodobenzenes combined with benzene thiols or iodobenzenes combined with o-bromo-benzene thiols were applied. These two approaches will provide an alternative for the synthesis of DBT derivatives.
Song, Juan,Wu, Hao,Sun, Wei,Wang, Songjiang,Sun, Haisen,Xiao, Kang,Qian, Yan,Liu, Chao
supporting information
p. 2083 - 2087
(2018/03/26)

A powder-based synthetic saisai anthracene method
A sample method for synthesis of thianthrene based on a sulfur powder comprises the steps: weighing 0.5 mmol of 1,2-diiodobenzene, 0.5 mmol of the sulfur powder, 0.05 mmol of cuprous iodide, 0.1 mmol of 1,10-phenanthroline and 1.0 mmol of potassium carbonate into a 25 mL round-bottom flask, adding a magnetic stirring bar and 2 mL of dimethyl sulfoxide, drying the obtained organic phase with anhydrous Na2SO4, filtering, evaporating to remove a solvent of the obtained filtrate, and separating and purifying the residue by silica gel column chromatography to obtain the thianthrene product. The method has the advantages: 1, raw materials are simple, and thiophenol or a derivative thereof having pungent smell has no need to be used; 2, the operation is simple, and any anhydrous and anaerobic operations and other special operations are not needed; and 3, reaction conditions are mild, the reaction can be completed by heating at 90 DEG C, and the thianthrene is suitable for magnified synthesis.
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Paragraph 0006; 0009; 0010; 0011

(2017/08/25)

Transformations of diphenyl sulfide and diphenylamine on aluminum chloride
Thianthrene has been synthesized by reacting diphenyl sulfide with AlCl3 in heptane at 98°C for 8 h at a diphenyl sulfide: AlCl3 molar ratio of 2: 1; the thianthrene yield is 58%. The reaction mechanism proposed previously has been confirmed by quantum-chemical calculations; the reaction is characterized by a low negative value of Gibbs free energy, a low heat of reaction, and a high activation energy of the first step. Diphenyl ether and diphenylamine do not enter the test reaction because of low nucleophilicity of the heteroatoms; diphenylamine dimerizes under the reaction conditions to form N,N′-diphenylbenzidine.
Nekhoroshev,Gubaidullin,Yarkova,Nekhorosheva,Nifant’ev,Voronkov,Poleshchuk, O. Kh.,Tarasova
p. 272 - 277
(2017/04/07)

Cu-catalyzed synthesis of diaryl thioethers and S -cycles by reaction of aryl iodides with carbon disulfide in the presence of DBU
Diaryl thioethers and S-cycles were obtained on the basis of the copper-catalyzed reaction of carbon disulfide and aryl iodides in the presence of DBU. This reaction enables the one-pot synthesis of diaryl thioethers by employing cheap, available, and easy-to-handle carbon disulfide with aryl iodides. The reaction was successfully employed in the construction of sulfur-containing cyclic molecules.
Zhao, Peng,Yin, Hang,Gao, Hongxin,Xi, Chanjuan
p. 5001 - 5006
(2013/06/27)

Synthesis of 2-styrylbenzoxazole derivatives by the reaction of styrylphenolic schiff bases with thianthrene cation radical
A simple and fast preparative method of 2-styrylbenzoxazoles by oxidative intramolecular cyclization of styrylphenolic Schiff bases with thianthrene cation (Th+.ClO4-) is described. The oxidative cyclization of Schiff bases in the presence of 2,6-di-tert-butyl-4- methylpyridine (DTBMP) gives 2-styrylbenzoxazole derivatives in better yields than those in the absence of DTBMP.
Park, Hee Jung,Park, Myeong Soon,Lee, Tae Hee,Park, Koon Ha
p. 663 - 667
(2013/06/27)

Oxidation-promoted activation of a ferrocene C-H bond by a rhodium complex
The oxidation of a rhodium(i) complex containing a ferrocene-based heterodifunctional phosphine N-heterocyclic carbene (NHC) ligand produces a stable, planar chiral rhodium(iii) complex with an unexpected C-H activation on ferrocene. The oxidation of rhodium(i) to rhodium(iii) may be accomplished by initial oxidation of ferrocene to ferrocenium and subsequent electron transfer from rhodium to ferrocenium. Preliminary catalytic tests showed that the rhodium(iii) complex is active for the Grignard-type arylation of 4-nitrobenzaldehyde via C-H activation of 2-phenylpyridine.
Labande, Agnes,Debono, Nathalie,Sournia-Saquet, Alix,Daran, Jean-Claude,Poli, Rinaldo
p. 6531 - 6537
(2013/07/26)

Magnetically separable CuFe2O4 nanoparticles catalyzed ligand-free C-S coupling in water: Access to (E)- and (Z)-styrenyl-, heteroaryl and sterically hindered aryl sulfides
An efficient coupling of styrenyl, heteroaryl and sterically hindered aryl halides with aryl- and heteroarylthiols catalyzed by the bimetallic Cu and Fe nanomaterial, CuFe2O4, in water in the presence of tetrabutylammonium bromide and potassium phosphate (K3PO4) has been achieved without using any ligand. A series of unsymmetrical functionalized (E)- and (Z)-styrenyl aryl, heteroaryl heteroaryl and sterically hindered aryl aryl sulfides has been obtained by this procedure. The compounds are obtained in high yields and excellent stereoselectivity has been observed for styrenyl sulfides. The catalyst can be easily separated by an external magnet and recycled for ten times without any appreciable loss of activity. This procedure provides an easy access to useful and challenging biologically active organosulfides which are difficult to achieve by other methods.
Kundu, Debasish,Chatterjee, Tanmay,Ranu, Brindaban C.
p. 2285 - 2296
(2013/10/01)

Synthesis of 'thianthrene dimer' by the coupling reaction of stannylthianthrenes in the presence of copper catalysts
The coupling reaction of 1-tributylstannylthianthrene (5) and 2-tributylstannylthianthrene (7) in the presence of copper catalysts at rt afforded the thianthrene dimer 1,1′-bithianthrene (3), 2,2′-bithianthrene (8), and 1,2′-dithianthrene (9) in high yields. Also we obtained thianthrene oxide dimer (R,R) (S,S)-1-(10-S-monoxythianthrene- 1-yl)thianthrene-10-S-monoxide (12) and (R,S) (S,R)-1-(10-S-monoxythianthrene-1- yl)thianthrene-10-S-monoxide (13) from 1-tributylstannyl-10-S-monoxythianthrene (10) under the same reaction condition. The final structural conformation of 3, 8, 9, and 12 was performed by X-ray crystallographic analysis. Further, the solvent effects in the coupling reactions were also examined.
Morita, Hiroyuki,Oida, Yasutaka,Ariga, Takamine,Fukumoto, Satoru,Sheikh, Md. Chanmiya,Fujii, Takayoshi,Yoshimura, Toshiaki
supporting information; experimental part
p. 4672 - 4679
(2011/06/26)

Ligand-free copper-catalyzed synthesis of diaryl thioethers from aryl halides and thioacetamide
Diaryl thioethers can be prepared via a copper-catalyzed cross-coupling between aryl halides and thioacetamide using Cs2CO3 as a base and DMSO-H2O as a solvent at 120 °C. Georg Thieme Verlag Stuttgart - New York.
Tao, Chuanzhou,Lv, Aifeng,Zhao, Nan,Yang, Shuai,Liu, Xiaolang,Zhou, Jian,Liu, Weiwei,Zhao, Jing
supporting information; experimental part
p. 134 - 138
(2011/03/22)

The first example of cation radical induced ether cleavage of benzyl phenyl ether
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Nam, Seong Yi,Han, Dong Sul,Lee, Wang Keun
scheme or table
p. 1467 - 1468
(2010/10/19)

Photo SN-bond cleavage and related reactions of thianthrene sulfilimine derivatives
Several 1- and 2-substituted thianthrene sulfilimine derivatives were prepared and the selectivity toward oxidation and N-tosylimination under several conditions was studied. In the photolysis of trans-5-(N-p-tosyl)iminothianthrene 10-oxide (trans-10), photo isomerization to cis-10 was observed. Further, photoimino-transfer reaction of sulfilimines and their 10-mono- and -dioxide derivatives to sulfides was intensively studied to make clear the ability as nitrene precursors.
Fujita, Tomoyuki,Kamiyama, Hideo,Osawa, Yasushi,Kawaguchi, Hiroyuki,Kim, Bung Ju,Tatami, Atsushi,Kawashima, Wataru,Maeda, Tetsuo,Nakanishi, Atsushi,Morita, Hiroyuki
p. 7708 - 7716
(2008/02/07)

Alkaline hydrolysis of N-bromoiminothianthrene derivatives
5-(N-Bromo)iminothianthrene (2) and 5-(N-bromo)iminothianthrene 10-oxide (5) and 10,10-dioxide (8) were prepared and their alkaline hydrolyses were studied. The compound 2 and cis-5-(N-bromo)iminothianthrene 10-oxide (cis-5) afforded the corresponding sulfoximine exclusively. While, unexpectedly, both trans-5-(N-bromo)iminothianthrene 10-oxide (trans-5) and 8 afforded mainly de-brominated products, trans-5-iminothianthrene 10-oxide (trans-4) and 5-iminothianthrene 10,10-dioxide (7), respectively. In these cases, 5-iminothianthrene 5,10-dioxide (6) (Z- and E-mixture) and 5-iminothianthrene 5,10,10-trioxide (9) and further de-iminated products were also formed respectively as minor products. The stereochemical considerations on the SN reactions are described in view of the steric effect and 'flip-flap' motion of the thianthrene framework.
Kawaguchi, Hiroyuki,Nakajima, Akitaka,Fujii, Takayoshi,Kim, Bung Ju,Hashimoto, Junko,Fujimoto, Akihiro,Yoshimura, Toshiaki,Morita, Hiroyuki
p. 10907 - 10913
(2007/10/03)

Adducts of thianthrene- and phenoxathiin cation radical salts with symmetrical alkynes. Structure and formation of cumulenes on alumina leading to α-diketones, α-hydroxyalkynes, and α-acetamidoalkynes
Thianthrene cation radical tetrafluoroborate (Th.+BF 4-) added to 2-butyne, 3-hexyne, 4-octyne, and 5-decyne in MeCN to form trans bisadducts E(Th+)C=C(Th+)R, where E = Me, Et, Pr, Bu (7a-d). Phenoxathiin cation radical tetrafluoroborate (PO .+BF4-) added similarly to the last three alkynes to form adducts E(PO+)C=C(PO+)E, 8b-d. Cyclic monoadducts were not found. The trans structures of 7 and 8 were deduced with X-ray crystallography (7c) and NME spectroscopy. When solutions of adducts in CHCl3 and MeCN were deposited on activated alumina, elimination of thianthrene (Th) and phenoxathiin (PO) occurred almost quantitatively. Detailed studies with (7b-d) indicated that a cumulene (15) was formed by the elimination of Th and that 15 was subsequently converted into small amounts of other products. In CHCl3, these products were the respective alkyne, thianthrene 5-oxide, an α-diketone (11), an α-hydroxyalkyne (12), and hydrogen. The same products were formed in MeCN along with an α-acetamidoalkyne (13). The formation of 15 and products derived from it is explained and was confirmed by preparation and reactions of 2,3,4-hexatriene.
Shine, Henry J.,Rangappa, Paramashivappa,Marx, John N.,Shelly, Dennis C.,Ould-Ely, Teyeb,Whitmire, Kenton H.
p. 3877 - 3883
(2007/10/03)

Polysulfane antitumor agents from o-benzyne. An odd-even alternation found in the stability of products o-C6H4Sx (x = 1-8)
Benzyne is shown to add elemental sulfur and give rise to a series of polysulfane compounds. A computational and experimental study is presented. Odd-membered o-C6H4Sx rings (x = 1-8), except x = 1, which suffers from ring strain, have enhanced stability compared to even-membered rings. The acquisition of odd-even data may shed new light, revealing patterns on polysulfane stability and structure.
Brzostowska, Edyta M.,Greer, Alexander
p. 5483 - 5485
(2007/10/03)

Decomposition of alkene adducts of thianthrene cation radical in nitrile solvents. Formation of alkyl-2-oxazolines and a new class of four-component products: 5-[(1-alkoxyalkylidene) ammonio]alkylthianthrenium diperchlorates
The monoadducts (4a-d) of thianthrene cation radical perchlorate (1a) and isobutene, 2-methyl-butene, 2-methyl-2-butene, and 2-methylpentene decompose spontaneously in acetonitrile (MeCN) solution, with the formation of thianthrene (Th). Decomposition of 4a (1,2-(5,10-thianthreniumdiyl)-2-methylpropane diperchlorate) and 4a', the corresponding dihexafluorophosphate, was studied in depth and extensively with 1H and 13C NMR spectroscopy. Decomposition of 4a was found to involve the solvent itself as well as water in the solvent, remaining from incomplete drying, and gave, apart from Th, successively, the perchlorate salts of 2,4,4-trimethyl-2-oxazoline (6) and 2-amino-2-methylpropyl acetate (7). These salts, 6-HCIO4 and 7-HCIO4, respectively, were prepared and used in understanding the reactions of 4a as well as the relationships among 6, 7, and 2-(acetylamino)-2-methyl propanol (8) in acidified MeCN solution. Decompositions of 4a-d in MeCN and other nitriles (RCN) containing an added alcohol (ROH) led to new products, 5-[(1-alkoxyalkylidene)ammonio]alkylthianthrenium diperchlorates (5a-u). These compounds were identified with 1H and 13C NMR spectroscopy and, in part, with X-ray crystallography and elemental analysis. The mechanisms of formation of 5-7 are discussed.
Shine, Henry J.,Zhao, Bing-Jun,Marx, John N.,Ould-Ely, Teyeb,Whitmire, Kenton H.
p. 9255 - 9261
(2007/10/03)

Nucleophilic reactions of 5-(aryl)thianthrenium bromides with sodium aryl oxides
Reactions between 5-(aryl)thianthrenium bromides (1a-e) with aryl (Ar) groups phenyl (a), p-tolyl (b), p-anisyl (c), p-chlorophenyl (d) and p-bromophenyl (e) and sodium aryl oxides (7a-c, Ar′ONa, Ar′ = phenyl, p-tolyl and p-chlorophenyl) were carried out in acetonitrile at 80°C. Results are compared with those of earlier reactions of 1a-e with corresponding sodium aryl thiolates (Ar′SNa). In contrast with the thiolate reactions, those with 7a-c were too slow at room temperature to be useful. Reactions of 1a-c at 80°C gave small amounts of benzene and toluene from la and b, small amounts of diaryl ethers ArOAr′ (9) and thianthrene (Th) and large amounts (90-97%) of 2-(ArS)-2′-(Ar′O)diphenyl sulfide (10). Compared with reactions of 1a-c, those of 1d and e gave larger amounts (10-17%) of 9, lesser amounts (25-30%) of 10 and substantial amounts (42-55%) of 2-[4-(Ar′O)-ArS]-2′-(Ar′O)diphenyl sulfide (12). Small amounts of 1,4-di(Ar′O)benzene (11) were also obtained from reactions of Id and e. Formation of 11 and 12 is preceded by replacement of halogen by Ar′O-. Structures of products 10 and 12 were deduced by comparison with earlier products from thiolate reactions, elemental analyses, mass spectrometry molecular masses and, in the case of 10, the crystal structure of 10d. It is proposed that products 9-12 are formed by nucleophilic reactions of Ar′O- at ipso positions in 1. Copyright
Qian, Ding-Quan,Shine, Henry J.,Thurston, John H.,Whitmire, Kenton H.
p. 142 - 147
(2007/10/03)

Mono- and bisadducts from the addition of thianthrene cation radical salts to cycloalkenes and alkenes
Thianthrene cation radical salts, Th.+ X-(X- = a, ClO4-; b, PF6-; c, SbF6-), add to cycloalkenes (C5-C8) in acetonitrile (MeCN) to form 1,2-bis(5-thianthreniumyl)cycloalkane salts and 1,2-(5,10-thianthreniumdiyl)cycloalkane salts, most of which have now been isolated and characterized. These are called bis- (3, 6, 9, 12) and monoadducts (4, 7, 10, 13). The proportional amount of the monoadduct obtained in the initial stage of the reaction varied with the cycloalkene in the order C6 ? C5 7 ? C8. Thus, the ratio bis:mono for C5 and C7 was, respectively, about 80/20 and 50/50. In contrast, only about 5% of the C6 monoadduct (7a) and none of 7b, c was obtained, while for C8 none of the bisadducts 12a-c was found. Bisadducts 3 and 9 lost thianthrene (Th) slowly in MeCN solution and changed into monoadducts 4 and 10. A comparable change from 6a into 7a was not observed. The monoadducts, themselves, lost a proton slowly in dry MeCN and opened into 1-(5-thianthreniumyl)cycloalkenes (5, 8, 11, 14). With 3 and 9, particularly, it was possible to follow with NMR spectroscopy the succession of changes, for example, 3 to 4 to 5. The opening of a monoadduct was made faster by adding a small amount of water to the solution. The bisadducts of 4-methylcyclohexene (15a) and 1,5- cyclooctadiene (17a) were isolated and characterized. Although a small amount of monodduct (16a) of 4-methylcyclohexene was found with NMR spectroscopy, it could not be isolated. Bis- and monoadducts were obtained also in additions of Th.+ ClO4- to acyclic alkenes, in relative amounts that, again, varied with the alkene. From cis-2-butene the dominant product was the bisadduct (18), while the monoaduct (19) was characterized with NMR spectroscopy but could not be isolated. In contrast, trans-3-hexene gave mainly the monoadduct (21), while the bis adduct (20) could not be isolated. With 4-methyl-cis-2-pentene, both bis- (22) and monoadduct (23) were isolated, the former being dominant. The conversion of 18 into 19 was characterized with NMR spectroscopy. In all cycloalkene bisadducts, the configurational relationship of the two thianthrenium groups was trans, while in the monoadducts, the bonds to the single thianthrene dication were (necessarily) cis. In both bis- and monoadducts of acyclic alkenes, the configuration of the alkene was retained. The mechanisms of addition with retention of configuration, of conversion of a bis- into a monoadduct, and of opening of a monoadduct are discussed. Products were identified with a combination of NMR spectroscopy, X-ray crystallography, elemental analysis, and (for cycloalkene adducts) reaction with thiophenoxide ion.
Qian, Ding-Quan,Shine, Henry J.,Guzman-Jimenez, Ilse Y.,Thurston, John H.,Whitmire, Kenton H.
p. 4030 - 4039
(2007/10/03)

Reactions of 5-(alkyl)thianthrenium and other sulfonium salts with nucleophiles
A series of 5-(alkyl)thianthrenium triflates (3a-d, g-i) with alkyl (R) groups Me (a), Et (b), isoPr (c), 2-Bu (d), cyclopentyl (g), cyclohexyl (h) and cycloheptyl (i) were prepared by alkylation of thianthrene (Th) with alkyl formate and trifluoromethanesulfonic (triflic) acid. Benzylation (3f) was achieved with benzyl bromide and silver triflate. 5-(Neopentyl)thianthrenium perchlorate (3e) was prepared by reaction of thianthrene cation radical perchlorate with dineopentyl mercury. Methyl- (4a) and cyclohexyldiphenylsulfonium triflate (4b) were made by alkylation of diphenyl sulfide. Benzyldimethyl- (5a), dibenzylmethyl- (5b) and benzylmethylphenylsulfonium perchlorate (5c) were prepared in standard ways. Reactions of these sulfonium salts with iodide ion and thiophenoxide ion were studied for comparison with our earlier reported reactions of comparable 5-(alkoxy)thianthrenium and methoxydiphenylsulfonium salts. It is deduced that reactions of 3-5 with nucleophiles (Nu-) I- and PhS- follow traditional SN2 and E2C paths. Thus, the salts 3a-c, e and f gave virtually quantitative yields of RNu and Th, while small amounts of butene(s) were obtained from 3d. The cycloalkyl salts 3g-i gave amounts of cycloalkylNu and cycloalkene typical of competition of SN2 and E2C routes in the classical reactions of cycloalkyl halides and tosylates with I- and PhS- ions. Whereas 4a gave only SN2 products, 4b gave SN2 and E2C products typical of SN2/E2C competition. Among the salts 5a-c displacement of the benzyl group was dominant (5a) or exclusive (5b, c), thus exhibiting the preferential displacement of a benzyl group that has been fully documented in earlier studies of SN2 reactions. Qualitative comparison showed that 3a (methyl) reacted much faster than 3e (neopentyl) with PhS-. Unlike alkoxysulfonium salts, the salts 3-5 do not appear to undergo reactions at the sulfonium sulfur atom. Copyright
Liu, Bo,Shine, Henry J.
p. 81 - 89
(2007/10/03)

One-step arylthiolation of aromatic compounds by disulfide radical cations generated from oxidation of diaryl disulfides with aluminium chloride
Reactions of di(phenyl and 4-tolyl) disulfides 1a and 1b with PhX 3a-e (X = H, Me, Et, Ph and Cl) in the presence of AlCl3 at 25°C give diaryl sulfides 4-6 by aromatic arylthiolation via the disulfide radical cations 2, along with thiophenols 7 formed in the incomplete reactions. Competitive intramolecular reactions of 2a also yield diphenyl sulfide 4a or/and thianthrene 8. However, the reactions of bis(4-chlorophenyl and 4-fluorophenyl) disulfides 1c and 1d selectively lead to the aromatic arylthiolation in high yields. The Hammett ρ = -8.8 at 25°C for the phenylthiolation in the reactions of 1a is more negative than that (ρ = -7.0 at -30°C) using SbCl5 instead of AlCl3, and the value ρ = -8.0 for the arylthiolation using 1d is less negative than that using 1a. These and the other mechanistic aspects support the arylthiolations via 2.
Takeuchi, Hiroshi,Suga, Keisuke
p. 1803 - 1808
(2007/10/03)

Thermolysis and photolysis of aryl thiocarbamate derivatives
Thermolysis of N-phenyl-O-phenylthiocarbamate (POPTC), N-phenyl-O-benzylthiocarbamate (POBTC), and N-phenyl-S-phenylthiocarbamate (PSPTC) by reflux for 15 hr at 220-230 °C affords degradation products assumed to be formed by homolysis at different sites f
Gaber,Aly,Fahmy
p. 243 - 251
(2007/10/03)

Reactions of nucleophiles with 5-(alkoxy)thianthrenium ions
Reactions of 5-(alkoxy)thianthrenium perchlorates (1) with weakly basic nucleophiles Br-, I- and PhS- (X-) in MeCN and DMSO led to SN2 substitution, E2C elimination, and reaction at sulfornium sulfur to extents depending on the structure of the alkoxy group (RO) in 1 and the nucleophile. Three types of reaction occurred with R = cyclopentyl (1a), cyclohexyl (1b), cis- (1c) and trans- 4-methylcyclohexyl (1d) and cycloheptyl (1e), and X- = Br and I-. That is, SN2 reaction gave RX and thianithrene 5-oxide (ThO), E2C reaction gave cycloalkene and ThO and reaction at sulfonium sulfur gave X2, thianthrene (Th) and cycloalkanol (ROH). Earlier work with R = Me (1f) and Et (1g) and X- = I-. Br- had shown that only SN2 reaction occurred. In contrast with reactions of halide ions, reactions of PhS- with 1b-g occurred only at sulfonium sulfur, giving Th, ROH and PhSSPh (DPDS). For comparison with 1, reactions of Ph2S+OMe (2) with I- and PhS- were carried out. Reaction with I- gave only Ph2S=O and Mel (SN2), Reaction with PhS- gave very little PhSMe (SN2) but mainly Ph2S, MeOH, and DPDS from reaction at sulfonium sulfur. The differences in nucleophilic pathways (PhS- vs Br- and I-) in reactions with 1 and 2 are attributed to differences in thiophilicities of the nucleophiles. The thiophilicity of PhS- dominates its reactions with 1 and 2. The direction toward products (Th, ROH and DPDS) in these reactions is compounded by the ease of displacement of alkoxide from 1 and 2 by PhS-, and the ease with which, subsequently, thiophilic PhS- attacks sulfenyl sulfur in the resulting phenylthiosulfonium ion. Copyright
Liu, Bo,Shine, Henry J.,Zhao, Wenyi
p. 827 - 836
(2007/10/03)

Complete regioselective formation of 2-(arylsulfinyl)diphenyl sulfides from 5-arylthianthreniumyl perchlorates
Treatment of 5-arylthianthreniumyl perchlorates with potassium tert- butoxide in dimethyl sulfoxide at room temperature gave 2- (arylsulfinyl)diphenyl sulfides (29-79% yields), which are the first examples for complete regioselective formation of S-monoxides from unsymmetrical arylthiodiphenyl sulfides.
Kim, Jongyup,Kim, Kab Sig,Kim, Kyongtae
p. 617 - 622
(2007/10/03)

UV-vis and IR spectroscopic characterization of diphenyl disulfide radical cation in acid zeolites and its rearrangement to thianthrenium radical cation
Adsorption of diphenyl disulfide (DPDS) from CH2Cl2 solutions onto acid zeolites at room temperature generated the "extended" radical cation, DPDS.+. At loadings of 3 wt%, oxidation to DPDS.+ is essentially complete. Upon heating the loaded zeolite to 200°C, the adsorbed DPDS.+ was converted into thianthrenium radical cation (TH.+). Ab initio calculations at the B3LYP and HF levels using the 6-31G* basis set suggest cyclization of a diphenyl disulfide-S,S-dication as a reasonable rate-determining step of the conversion. Non-acidic zeolites devoid of Lewis and Bronsted sites (as determined by the pyridine adsorption-desorption method) failed to generate DPDS.+ to an extent detectable spectroscopically: these results support Lewis and/or Bronsted sites as being responsible for the observed oxidation.
Marti, Vicente,Fernandez, Lorenzo,Fornes, Vicente,Garcia, Hermenegildo,Roth, Heinz D.
p. 145 - 152
(2007/10/03)

Primary and secondary 5-(alkyloxy)thianthrenium perchlorates. Characterization with 1H NMR spectroscopy, reactions with iodide and bromide ion, and thermal decomposition in solution
A series of 5-(alkyloxy)thianthrenium perchlorates has been made in which the alkyl group is primary (1a-1p) and secondary (2a-2g). Preparations were carded out by reaction of the corresponding alkanol with thianthrene cation radical perchlorate in CH2Cl2 solution followed by precipitation of the perchlorate salt with dry ether. 1H NMR spectroscopy reveals that the presence of a stereogenic center in the alkyl group causes inequivalence in the ordinarily paired protons (e.g., H-4, H-6) of the thianthrenium ring. Reaction of iodide and bromide ion with primary alkyl-group compounds (e.g., methyl, ethyl, propyl, butyl) gave the alkyl halide in very good yield and by a second-order kinetic displacement. The second product was thianthrene 5- oxide (ThO). Rate constants for some of these reactions are reported. Reaction of secondary alkyl group compounds (e.g., 2-propyl, 2-pentyl, 2- hexyl, and 3-hexyl) with iodide ion gave good yields of alkyl iodide but also increasing evidence for a side reaction at the sulfonium sulfur, leading to I2, thianthrene, and secondary alkanol. Decomposition of some compounds at 100°C in solution (acetonitrile or 1,2-dichloroethane) was studied and gave alkene(s) and ThO.
Zhao, Wenyi,Shine, Henry J.
p. 695 - 702
(2007/10/03)

Synthesis of 2,3,8,9-Dibenzo-5,6-(substituted)benzo-1,4-dithio-7-oxacyclonona-2,5,8-trienes and Some Electrophilic Substitution Reactions
Treatment of 5-(2-hydroxyaryl)thianthreniumyl perchlorates 1 with sodium hydride in tetrahydrofuran at reflux gave the title compounds 5 in excellent yields. For the reactivities of the compounds 5, the selected compounds 5 were subjected under the conditions of electrophilic substitution reactions. Bromination of 5,6-[3-(2-butyl)benzo)-2,3,8,9-dibenzo-1,4-dithio-7-oxacyclonona-2,5,8-triene (5f) in acetic acid at 60° afforded two bromo compounds 9 (22%) and 10 (69%), which were oxidized by m-chloroperbenzoic acid to give tetraoxides 11 (95%) and 12 (97%), respectively. Treatment of 5f with acetyl chloride in the presence of aluminum chloride in carbon disulfide at 0° gave an acetylated compound 13 (58%). Nitration of 5f with nitric acid in acetic acid at 50° gave a nitro compound 17 (15%) together with 1,4-dioxide 7e (22%) and a 5-oxide 18 (3%) whose regiochemistry has not been established. On the other hand, 5,6-(3-methylbenzo)-2,3,8,9-dibenzo-1,4-dithio-7-oxacyclonona-2,5,8-triene (5a) reacted with acetyl chloride under the same conditions to give two acetylated compounds 15 (33%) and 16 (18%). The mechanism for the formation of 5 and the structural elucidation of these compounds are discussed.
Kim, Man Nyoung,Kim, Kyongtae
p. 235 - 247
(2007/10/03)

Characterization of polycyclic aromatic hydrocarbon particulate and gaseous emissions from polystyrene combustion
The partitioning of polycyclic aromatic hydrocarbons (PAHs) between the particulate and gaseous phases resulting from the combustion of polystyrene was studied. A vertical tubular flow furnace was used to incinerate polystyrene spheres (100-300 μm) at different combustion temperatures (800- 1200 °C) to determine the effect of temperature and polystyrene feed size on the particulate and gaseous emissions and their chemical composition. The furnace reactor exhaust was sampled using real-time instruments (differential mobility particle sizer and/or optical particle counter) to determine the particle size distribution. For chemical composition analyses, the particles were either collected on Teflon filters or split into eight size fractions using a cascade impactor with filter media substrates, while the gaseous products were collected on XAD-2 adsorbent. Gas chromatography/mass spectroscopy (GC/MS) was used to identify and quantify the specific PAH species, their partitioning between the gas and particulate phases, and their distribution as a function of emission particle size. The total mass and number of PAH species in both the particulate and gas phases were found to decrease with increasing incineration temperature and decreasing polystyrene feed size, while the mean diameter of the particles increases with increasing incineration temperature and decreasing feed size. In addition, the PAH species in the particulate phase were found to be concentrated in the smaller aerosol sizes. The experimental results have been analyzed to elucidate the formation mechanisms of PAHs and particles during polystyrene combustion. The implications of these results are also discussed with respect to the control of PAH emissions from municipal waste-to-energy incineration systems. The partitioning of polycyclic aromatic hydrocarbons (PAHs) between particulate and gaseous phases resulting from the combustion of polystyrene was studied. A vertical tubular flow furnace was used to incinerate polystyrene spheres to determine the effect of temperature and polystyrene feed size on the particulate and gaseous emissions and their chemical composition. The furnace reactor exhaust was sampled using real-time instruments to determine the particle size distribution. The total mass and number of PAH species in both the particulate and gas phases were found to decrease with increasing incineration temperature and decreasing polystyrene feed size, while the mean diameter of the particles increases with increasing incineration temperature and decreasing feed size. In addition, the PAH species in the particulate phase were found to be concentrated in the smaller aerosol sizes.
Durlak, Susan K.,Biswas, Pratim,Shi, Jichun,Bernhard, Mary Jo
p. 2301 - 2307
(2007/10/03)

Development of a dual-electrolysis stopped-flow method for the observation of electrogenerated chemiluminescence in energy-sufficient systems
New methodology for the measurement of electrogenerated chemiluminescence (ECL) has been developed by using a dual-electrolysis stopped-flow system. Using this method, the ECL from 'energy-sufficient' systems composed of different kinds of ion radicals can be easily observed by mixing both the electrolyzed solutions directly. The apparatus and method have been described in detail as well as the ECL observations for various energy-sufficient systems. In particular, in the reaction between the thianthrene (TH) cation radical and the pyrene (PY) anion radical, it was found that the emission spectra changed with the addition of the precursors, reflecting both complex electron- and energy-transfer processes in solution. The present results indicate that the electron- and energy-transfer reactions changed significantly, depending on the type of molecules. The ECL observation with the addition of the third molecule was also informative to compare the ease of the formation of the excited states. It was clarified that the excited states of 9,10-diphenylanthracene and rubrene are easily formed compared with those of TH and PY.
Oyama, Munetaka,Okazaki, Satoshi
p. 5079 - 5084
(2007/10/03)

Thermal rearrangement of aromatic acetal and thioacetal derivatives
Thermolysis of benzaldehyde dibenzyl acetal 1 by refluxing at 250°C for 3 days give H2O, toluene, benzaldehyde, benzyl alcohol, bibenzyl, stilbene and benzylphenylcarbinol. Similar treatment of cinnamaldehyde diphenyl thio-acetal 2 furnishes H2S, bibenzyl, toluene, stilbene, thiophenol, diphenyl sulfide, indene, thianthrene, 2,3,4,5-tetraphenylthiophene and polystyrene. Moreover thermolysis of 1 in the presence of isoquinoline gives 1-benzylisoquinoline in addition to the previous products. From these results a free radical mechanism has been postulated to take place through the initial homolysis of different bonds in the acetal molecules.
Gaber,Aly
p. 657 - 661
(2007/10/03)

Structure and Thermal Decomposition of Some 5-(Cyclohexyloxy)thianthreniumyl Perchlorates
Five sets of cis- and trans-substituted cyclohexanols were used for reaction with thianthrene cation radical perchlorate, namely, cis- and trans-cyclohexane-1,2-diol, cis- and trans-2-methyl-, 3-methyl-, and 4-methylcyclohexanol, and cis,cis- and trans,trans-3,5-dimethylcyclohexanol. Reaction in CH2-Cl2 solution and precipitation with ether gave the corresponding crystalline 5-(cyclohexyloxy)-thianthreniumyl perchlorate salts. The configuration of each salt in CDCl3 was shown by 1H and 13C NMR spectroscopy to correspond with the configuration of the cyclohexanol from which it was made. X-ray Ortep diagrams of four of the salts confirmed the structure deduced from NMR spectroscopy. In the NMR, inequivalence of the 1H and 13C signals from the thianthreniumyl 4-and 6-, 1- and 9-, 2- and 8-, and 3- and 7-positions was found when the 1′-position of the cyclohexyl ring was stereogenic. In the four Ortep diagrams, the orientation of the S-O bond was psuedoaxial. Thermal decomposition of the salts made from the monosubstituted cyclohexanols at 100°C in CH3CN solution gave products consistent with the assigned structures.
Zhao, Wenyi,Shine, Henry J.,Whittlesey, Bruce R.
p. 8693 - 8701
(2007/10/03)

Probing for Electronic and Steric Effects in the Peracid Oxidation of Thianthrene 5-Oxide
A systematic examination of the electronic and steric effects in the peracid oxidation of thianthrene 5-oxide (SSO) was undertaken and has revealed valuable information on the oxidative reactivity of the SSO mechanistic probe toward peroxidic oxidants. Thus, no significant steric effect was found on the bisulfoxide (SOSO)/sulfone (SSO2) product ratio for aliphatic peracids with varying size of alkyl groups [R = Me, Et, i-Pr, t-Bu, (n-Bu)(Et)CHCH2]. However, a significant electronic effect was observed for CH3CO3H and CF3CO3H, for which the Xso values were 0.16 and 0.01, i.e., predominant oxidation of the sulfide functionality to the SOSO product by these oxidants. In addition, substituted perbenzoic acids displayed this trend. In contrast, the nucleophilic peracid anion led exclusively (Xso = 1.00) to oxidation of the sulfoxide site to the SSO2 product. The oxygen transfer appears to be orbital-controlled since the more electrophilic oxidant is clearly the more reactive as well as more chemoselective, i.e., preferred attack at the more nucleophilic sulfide site in SSO.
Adam, Waldemar,Golsch, Dieter
p. 115 - 119
(2007/10/03)

ONE STEP SYNTHESIS OF POLYARYLTHIOETHERS CONSISTING OF ORTHO-PHENYLTHIO MOIETY
The reactions of 5-arylthianthrenium perchlorates with sodium hydrosulfide hydrate (NaSH*xH2O) in aqueous THF at reflux afforded polyarylthioethers having five sulfur atoms bonded to only ortho positions of each aryl group in good to excellent yields.
Shin, Song Seok,Kim, Man Nyoung,Kim, Hyun Ock,Kim, Kyongtae
p. 8469 - 8472
(2007/10/02)

Reactions of Phenols with Thianthrene Cation Radical
The phenols 2-R1-6-R2-phenol 1a-g in which R1 = R2 = tert-butyl, methyl, isopropyl, Cl, Br, F, and H reacted with thianthrene cation radical perchlorate (TH+ClO4-) 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.The 2,6-di-tert-butyl-4-R3-phenols 4a-c, R3 = tert-butyl, methoxy, and methyl, reacted with Th+ClO4- in nitrile solvents (RCN) to give 2-R-5-R3-7-tert-butylbenzoxazoles 5a-e.The tert-butyl group that was displaced by RCN in forming 5 was converted into t-BuNHCOR (8), tert-butyl alcohol, and isobutene.In contrast, 2-tert-butyl-4,6-dimethylphenol (9) gave, in CH3CN, 4-tert-butyl-2,5,7-trimethylbenzoxazole (11), that is, with migration of the displaced tert-butyl group.The reactions of 4-tert-butylphenol (14) and 2,4-di-tert-butylphenol (17) are also described.
Shin, Seung-Rim,Shine, Henry J.
p. 2706 - 2710
(2007/10/02)

PYROLYSIS OF ARYL DESYL SULFIDE
Phenyl desyl sulfide on pyrolysis by heating at 250 deg C for 15 hours, gives H2S, benzaldehyde, benzil, bibenzyl, stilbene, thiophenol, diphenyl sulfide, thianthrene and 2,3,4,5-tetraphenylthiophene.Analogous results were also obtained on pyrolysis of p-tolyl desyl sulfide under the same conditions in addition to H2O, p-ditolyl sulfide, thio p-cresol, p-bitolyl and 2-phenylbenzothiophene.The observed results has been interpreted in terms of a free radical mechanism involving homolysis of C-S bond.Key words: Pyrolysis; aryl desyl sulfide.
Gaber, A. M.,Abbady, M. S.
p. 7 - 12
(2007/10/02)

THERMOLYSIS AND PHOTOLYSIS OF SOME SELECTED ARYL THIOESTERS
Aryl thioesters I and II were prepared and pyrolyzed in the absence of promotors either alone or in isoquinoline as solvent.Thermolysis of β-naphthyl thiobenzoate (I) on heating in air at 250 deg C gives benzil, benzophenone, benzoic acid, biphenyl, thio β-naphthol, 2,2'-binaphthyl, diphenyl sulfide, thianthrene, thiophenol, phenyl β-naphthyl sulfide and 2,2'-binaphthyl sulfide.Similar results were also obtained on heating p-tolyl thiobenzoate (II) under the same conditions in addition to thio p-cresol, p-bitolyl, p-ditolyl sulfide and phenyl p-tolyl sulfone.H2S and CO are also produced in all cases.Thermolysis of I and II in the presence of isoquinoline affords in addition to the above products, 1-phenylisoquinoline.Photolysis of I and II in acetone gives similar products to those of the thermolysis.From these results a free radical mechanism has been postulated to take place through the initial homolysis of C-S bond.No isomer redistribution proceeds the coupling reactions.Key words: Thermolysis, photolysis, aryl thioesters.
El-Aal, Abd,Gaber, M.
p. 211 - 217
(2007/10/02)

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= C6H5; 1b, R= 4-CH3C6H4; 1c, R= 4-NO2C6H4; 1d, R= 4-CH3OC6H4; 1e, R= 2-CH3OC6H4; 1f, R= 1-naphthyl; 1g, R= C5H11; 1h, R= C4H9), with thianthrene cation radical perchlorate (Th.+ClO4-) in acetonitrile under argon were studied.The major product from the oxime in all cases, but of 1d, was the nitrile, RCN.The anticipated product of oxidative cycloaddition, namely, a 3-R-5-methyl-1,2,4-oxadiazole (2), was obtained in substantial yield (2d, 66percent) only in the case of 1d.An isomeric 5-R-3-methyl-1,2,4-oxadiazole (3) was obtained from some reactions, that is, 3c alone from 1c, and a mixture of 2a and 3a from 1a.Neither 2 nor 3 was obtained in measurable amounts from reactions of 1g and 1h.The aldehyde (RCHO) was obtained in small yields from each reaction.Thianthrene (Th) and thianthrene 5-oxide (ThO) were also major products.Studies with -1b and -1d showed that the oxgen atom in 2 came entirely and in ThO primarily from the oxime.Studies of workup with H218O showed that the workup water was the source of the oxgen atom in RCHO and to a small extent in ThO.Explanations are given for the formation of 2 by a stepwise addition of RCH=NOH.+ (1.+) to solvent nitrile and of 3 by the reaction of solvent nitrile with an oxaziridine cation radical (7, obtained from 1.+).
Chiou, Shishue,Hoque, A. K. M. M.,Shine, Henry J.
p. 3227 - 3232
(2007/10/02)

Evidence for Electron Transfer in Reactions of Thianthrene Cation Radical with Dialkylmercurials
Reactions of dialkylmercurials (R2Hg) with thianthrene cation radical perchlorate (Th.+ClO4-) in acetonitrile solution have been studied in quantitative detail.Evidence was obtained from reactions of MeHgR (R = Et, i-Pr, tBu) that reaction begins with electron transfer rather than with electrophilic cleavage of an alkyl-mercury bond.That is, each reaction gave MeHg+ and R., diagnostic of the formation and decomposition of MeHgR.+, rather than 5-methylthianthreniumyl perchlorate (1a), which would have been diagnostic of electrophilic displacement of the least hindered group (Me).The radicals R. either were trapped at the sulfur atom of Th.+ to form a 5-alkylthianthreniumyl perchlorate (Et., 1b) and at the ring positions of Th.+ to form 1- and 2-alkylthianthrenes (Et., i-Pr.) or were oxidized to the cations R+ (Et., i-Pr., and t-Bu.).Products of R+ were obtained, after workup with 4 M aqueous LiCl, as alkene, ROH, RNHCOCH3 and RCl.These reactions had the stoichiometric ratio of reactants 2Th.+ClO4-/MeHgR.Reactions of symmetrical R2Hg sometimes followed this stoichiometry (R = Me, Et, Bu) and led to RHg+ and 5-R-thianthreniumyl perchlorates (1a,b,e).Other R2Hg (R = t-Bu, benzyl, allyl) underwent oxidation by 4 equiv of Th.+ClO4-.Di-tert-butyl- and dibenzylmercury gave products derived entirely from the respective cation, R+.Diallylmercury gave some of the sulfonium product, 5-allylthianthreniumyl perchlorate (1g).None of the reactions with R = i-Pr, t-Bu, and benzyl led to the isolation of a thianthreniumyl perchlorate (i.e., 1c,d,f).Oxidations at the 4:1 molar ratio produced Hg(ClO4)2, which formed a partly insoluble complex (2) with thianthrene having the composition Th3Hg(ClO4)2.This product could be isolated if removed before workup treatment with aqueous 4 M LiCl, which, otherwise caused its decomposition into its components.The complex 2 was also prepared directly from reaction of Th with Hg(ClO4)2 in acetonitrile.Oxidation of benzylmercuric chloride by Th.+ClO4- in methylene chloride solution also occurred quantitatively, giving benzyl chloride, 1- and 2-benzylthianthrene, and a mixture of dibenzylthianthrenes.Oxidation of t-BuHgCl in acetonitrile solution led to a quantitative mixture of isobutene, t-BuOH, and t-BuNHAc.Th.+ClO4- also oxidized metallic Hg to either Hg+ or Hg2+, depending on the amount of oxidant used.
Lochynski, Stanislaw,Shine, Henry J.,Soroka, Miroslaw,Venkatachalam, T. Krishnan
p. 2702 - 2713
(2007/10/02)

Reactions of Phenylmagnesium Chloride and Phenyllithium with Thianthrene Cation Radical Perchlorate. Evidence for Electron Transfer: Formation and Decomposition of 5-Substituted Thianthreniumyl Perchlorates
Reaction of thianthrene cation radical perchlorate (Th+ClO4-), suspended in either ether or THF, with PhMgCl, and reaction of Th+ClO4-, suspended in ether, with PhLi in C6H12/ether, gave largely benzene and Th. 5-Phenylthianthreniumyl perchlorate (1a) was formed in the Grignard reactions but was not obtained in the PhLi reaction.Diphenyl sulfide (Ph2S) and dibenzothiophene (DBT) were obtained with PhMgCl and PhLi in ether, but not with PhMgCl in THF.Small amounts of ethyl 1-phenylethyl ether and 2-phenylethyltetrahydrofuran (PhTHF) were also formed.Reaction with PhMgCl in THF-d8 and with PhLi in (C2D5)2O gave a mixture of C6H6 and C6H5D.These results show that phenyl radical (Ph) was formed in the cation radical reactions and abstracted H(D) atom from the solvent.The results suggest also that Ph was trapped by Th+, leading to 1a.However as shown with control reactions, 1a reacted further with PhMgCl (slowly) and PhLi (rapidly) and was converted into Ph2S and DBT.Control reaction of PhLi with 1a gave Ph2S and DBT in high, approximately equal yields.Reaction with 5-(p-tolyl)thianthreniumyl perchlorate (1b) analogously gave phenyl p-tolyl sulfide and DBT.Reaction of PhMgCl with 1a was slow and incomplete and gave not only Ph2S and DBT but also some 2-phenyl-2'-(phenylthio)diphenyl sulfide (2a) and a mixture of 1- and 2-phenylthianthrene (together designated as 3a).An analogous reaction occured between PhMgCl and 1b.Reaction of 1a with BuMgCl gave BuSPh and DBT, some 2-(phenylthio)diphenyl sulfide (4), and some 2-(butylthio)-2'-phenyldiphenyl sulfide (5a).In contrast, reaction of PhMgCl with 5-butylthianthreniumyl perchlorate (1e) gave mainly benzene and Th, while reaction of BuMgCl with 1e gave mainly butane, octane, and Th analog with a small amount of 2-butyl-2'-(butylthio)diphenyl sulfide (5e).Reaction of PhLi with 1e and its analogues 5-methyl- and 5-ethylthianthreniumyl perchlorate (1c and 1d, respectively) gave benzene, Th, the corresponding alkyl phenyl sulfide and DBT, and small amounts of 2-(alkylthio)-2'-phenyldiphenyl sulfide (2c-e).Formation of benzene in these reactions is attributed to deprotonation of the alkyl group in 1c-e and concomitant formation of an ylide (6-8).Ylide 6, from reaction of PhLi with 1c, was trapped by reactions with subsequently added water and phenol (reconverting 6 to 1c) and with added benzophenone, leading to Th and 1,1-diphenyloxirane (9).Diphenylmercury did not react with 1a in acetonitrile solution.The apparent complexity of reactions of Th+ClO4- with PhMgCl and PhLi is better understood in the light of knowledge about reactions of 1a-e.The comparative simplicity of reaction of Th+ClO-, with Ph2Hg is also made clearer.
Boduszek, Bogdan,Shine, Henry J.,Venkatachalam, T. Krishnan
p. 1616 - 1626
(2007/10/02)

meso-Tetraphenylporphinatoiron Catalysed Reductive Cleavage of some S-O, S-N, and S-C Bonds in Sulphoxides and Sulphilimines
meso-Tetraphenylporphinatoiron chloride (TPPFeIIICl) has been found to catalyse the reductive cleavage of semipolar S-O and S-N bonds in aromatic sulphoxides and sulphilimines respectively with both 1-benzyl-1,4-dihydronicotinamide (BNAH) and sodium borohydride.Sulphoxides bearing electron-withdrawing substituents are much more readily reduced than those with electron-donating groups.The rate of reduction by the TPPFeIII/BNAH system decreases in the following order: N-unsubstituted sulphilimines > N-tosylsulphilimines > aromatic sulphoxides.During the reaction with sulphoxides, the formation of the μ-oxo dimer of TPPFeIII has been observed.Under the same conditions, concurrent reductive cleavage of the S-C bond was observed with sulphoxides bearing an electron-withdrawing group at the α-position.Control experiments revealed that the reductive S-dealkylation of these sulphides is accompanied by the major S-deoxygenation reaction.Plausible mechanisms are discussed.
Nagata, Toshiyuki,Fujimori, Ken,Yoshimura, Toshiaki,Furukawa, Naomochi,Oae, Shigeru
p. 1431 - 1435
(2007/10/02)