110-06-5Relevant articles and documents
Thermal rearrangement of terf-butylsulfinamide
Arava, Veera Reddy,Gorentla, Laxminarasimhulu,Dubey, Pramod Kumar
, p. 9 - 12 (2011)
tert-Butylsulfinamides are unstable above room temperature, and in chlorinated solvents they undergo rearrangement to form the more stable N-(tert-butylthio)-tert-butylsulfonamide.
The Titanium Dioxide Sensitised Photo-Oxidation of Sulphides
Davidson, R. Stephen,Pratt, Julie E.
, p. 5903 - 5906 (1983)
Titanium dioxide has been shown to photosensitise the oxidation of sulphides to give sulphoxides and sulphones.Evidence is presented against the involvement of singlet oxygen and in favour of the sulphide radical cations as being intermediates.
A New and Practical Method of Decarboxylation: Photosensitized Decarboxylation of N-Acyloxyphthalimides via Electron-Transfer Mechanism
Okada, Keiji,Okamoto, Kazushige,Oda, Masaji
, p. 8736 - 8738 (1988)
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Synthesis and decomposition of some dialkyl oxide derivatives of organotrisulfides
Derbesy, Gerard,Harpp, David N.
, p. 991 - 997 (1996)
The isolation or detection of sulfenic sulfonic thioanhydrides 1 (e.g., 6), sulfenyl vic-disulfoxides 4 (e.g., 9, 14), and sulfinic thioanhydrides 5 (e.g., 20) has been carried out by oxidative procedures at various temperatures. The decomposition of these compounds has been investigated and is shown to be consistent with the mechanism proposed for the decomposition of trisulfide monoxides.
The rapid and efficient synthesis of disulfides from alkyl and acyl halides
Tajbakhsh, Mahmood,Lakouraj, Moslem M.,Mahalli, Majid S.
, p. 1453 - 1456 (2008)
Various symmetrical dialkyl and diacyl disulfides are prepared easily in high yields from the corresponding alkyl and acyl halides under mild and nonaqueous conditions using N,N'-dibutyl-N,N,N',N'-tetramethyl- ethylenediammonium tetrahydroborate (BTMETB) or N,N'-dibenzyl-N,N,N',N'- tetramethylethylenediammonium tetrahydroborate (BZTMETB) and elemental sulfur. The quaternary diammonium borohydrides were easily prepared by treatment of the corresponding quaternary diammonium chloride or bromide with alkaline solution of sodium borohydride at room temperature.
CATALYTIC OXIDATION OF THIOLS BY COENZYME PQQ
Itoh, Shinobu,Kato, Nobuyuki,Ohshiro, Yoshiki,Agawa, Toshio
, p. 135 - 136 (1985)
Oxidation of thiols by coenzyme PQQ as a new enzymatic oxidation-reduction model was found to proceed catalytically under aerobic conditions to give corresponding disulfides.
REACTION OF SULFUR DIOXIDE WITH THIOLS CATALYZED BY BORON TRIFLUORIDE ETHERATE. EVIDENCE FOR A POSSIBLE INTERVENTION OF DITHIOSULFITE AS A REACTION INTERMEDIATE.
Akiyama
, p. 2657 - 2660 (1983)
The reaction of sulfur dioxide (SO//2) with 1-propanethiol (NPT), 2-propanethiol (IPT), or 2-methyl-2-propanethiol (TBT) catalyzed by boron trifluoride ethrate (BF//3OEt//2) was investigated. The ratios of dialkyl trisulfide to dialkyl disulfide obtained (RSSSR/RSSR) at an early stage of the reaction were larger than 1 for the reaction of TBT and less than 1 for the reaction of NPT or IPT. The reaction of dithiosulfites with BF//3OEt//2 in the presence or absence of thiol was investigated. From a consideration of the similarity of the composition of the sulfides formed in the reaction of dithiosulfites with BF//3OEt//2 to those in the reaction of SO//2 witn thiol in the presence of BF//3OEt//2, the possibility of the intervention of dithiosulfite as a reaction intermediate in the reaction of SO//2 with thiol is discussed.
Oxidation of thiols to bisulfides by elemental sulfur without contamination by higher polysulfides
Shaw, James E.,McAfee, Marilyn G.
, p. 125 - 131 (1998)
Dialkyl disulfides were prepared in near quantitative yield by oxidation of alkanethiols with elemental sulfur using NaOH and ethoxylated alcohols as catalysts. Tergitol 15-S-7 was one of several ethoxylated alcohols which was used. Contamination by trisulfides was essentially eliminated in the disulfide products. The ratios of disulfide to trisulfide ranged from 100/0 to 99.6/0.4 for reactions with primary and secondary alkanethiols (100% excess) such as 1-propanethiol, 1-octanethiol, 2-propanethiol, and 2-butanethiol. The process did not work for tertiary alkanethiols such as 2-methyl-2-propanethiol where the trisulfide was greatly favored.
Thiol Anions in Nucleiphilic Aromatic Substitution Reactions with Activated Aryl Halides. Attack on Carbon vs Attack on Halogen
Montanari, Stefano,Paradisi, Cristina,Scorrano, Gianfranco
, p. 5628 - 5631 (1993)
The reaction of o-iodonitrobenzene with thiol anions (RSNa, R = Me, 2-Pr, t-Bu) in 2-propanol solution produces the o-nitrophenyl thioether and nitrobenzene in relative proportions and with rates which depend on R.The results of kinetic analysis and of D-incorporation experiments are inconsistent with a radical chain mechanism as proposed earlier for the alkoxide-promoted hydro-de-halogenation of aryl halides.The data clearly indicate the involvement of a carbanionic intermediate (the o-nitrophenyl anion) and are consistent with a stepwise mechanism in which the first step is nucleophilic attack on iodine to form a sulphenyl halide and the o-nitrophenyl anion (a halogenophilic reaction).In contrast, the reaction of the other o-halonitrobenzenes (F, Cl, Br) produces exclusively the product of alkylthio-de-halogenation according to the addition/elimination (SNAr) mechanism.The fact that in these systems the reactivity of thiol anions results from their ability as bielectronic nucleophiles rather than as reducing agents is discussed.
Photocatalytic Aerobic Thiol Oxidation with a Self-Sensitized Tellurorhodamine Chromophore
Lutkus, Luke V.,Rettig, Irving D.,Davies, Kellie S.,Hill, Jacqueline E.,Lohman, James E.,Eskew, Mathew W.,Detty, Michael R.,McCormick, Theresa M.
, p. 2588 - 2596 (2017)
Aerobic oxidation of thiols to disulfides was achieved photocatalytically using a tellurorhodamine chromophore (9-mesityl-3,6-bis(dimethylamino)telluroxanthylium hexafluorophosphate) as both the sensitizer and catalyst. The proposed mechanism, supported experimentally and computationally with DFT, involves the formation of a tellurorhodamine telluroxide from reaction with water and singlet oxygen generated by irradiation of the tellurorhodamine. The oxidation to the telluroxide is accompanied by the formation of hydrogen peroxide. The telluroxide oxidizes thiols to regenerate the tellurorhodamine and the disulfide plus water. Mechanistically, DFT suggests adding two thiols to the telluroxide with the loss of H2O to give a trigonal-bipyramidal Te(IV), which undergoes concerted loss of disulfide to regenerate 1. Oxidation of thiophenol and 2-naphthalenethiol was complete after 2 h of irradiation with visible light under atmospheric conditions. Oxidation of the electron-poor 2,6-dichlorothiophenol, the sterically bulky tert-butylmercaptan, and aliphatic dodecanethiol was slower. The two aliphatic thiols displayed competing catalyst degradation. The corresponding selenorhodamine chromophore (9-mesityl-3,6-bis(dimethylamino)selenoxanthylium hexafluorophosphate) does not form the corresponding selenoxide under similar conditions and photooxidizes thiophenol and 2-naphthalenethiol much more slowly (≤6% conversion after 2-3 h).
Theoretical and electrochemical analysis of dissociative electron transfers proceeding through formation of loose radical anion species: Reduction of symmetrical and unsymmetrical disulfides
Antonello, Sabrina,Benassi, Rois,Gavioli, Giovanna,Taddei, Ferdinando,Maran, Flavio
, p. 7529 - 7538 (2002)
The dissociative reduction of a series of symmetrical (RSSR, R = H, Me, t-Bu, Ph) and unsymmetrical disulfides (RSSR′, R = H, R′ = Me and R = Ph, R′ = Me, t-Bu) was studied theoretically, by MO ab initio calculations and, for five of them, also experimentally, by convolution voltammetry in N,N-dimethylformamide. The reduction is dissociative but proceeds by a stepwise mechanism entailing the formation of the radical anion species. The electrochemical data led to estimated large intrinsic barriers, in agreement with an unusually large structural modification undergone by the disulfide molecules upon electron transfer. The theoretical results refer to MP2/3-21G*//MP2/3-21G*, MP2/3-21*G*//MP2/3-21G*, CBS-4M, and G2(MP2), the latter approach being used only for the molecules of small molecular complexity. A loose radical-anion intermediate was localized and the dissociation pattern for the relevant bonds analyzed. For all compounds, the best fragmentation pathway in solution is cleavage of the S-S bond. In addition, S-S bond elongation is the major structural modification undergone by the disulfide molecule on its way to the radical anion and eventually to the fragmentation products. The calculated energy of activation for the initial electron transfer was estimated from the crossing of the energy profiles of the neutral molecule and its radical anion (in the form of Morse-like potentials) as a function of the S-S bond length coordinate. The inner intrinsic barrier obtained in this way is in good agreement with that determined by convolution voltammetry, once the solvent effect is taken into account.
A Mild, High-Yield Conversion of Thiols into Disulfides Using Disulfide Dication Salt: A New Redox System
Fujihara, Hisashi,Akaishi, Ryouichi,Furukawa, Naomichi
, p. 616 - 617 (1989)
A new redox reaction of thiols with disulfide dication salt, 1,5-dithioniabicyclooctane bis(trifluoromethanesulfonate), under mild conditions gave the corresponding disulfides in good yields together with 1,5-dithiacyclooctane.
4,4'-Azopyridine as an easily prepared and recyclable oxidant for synthesis of symmetrical disulfides from thiols or alkyl halides(tosylates)/thiourea
Khalili, Dariush,Iranpoor, Nasser,Firouzabadi, Habib
, p. 544 - 555 (2015)
Heterocyclic azo compounds, prepared from corresponding amines in one step, are used as effective oxidants for the conversion of thiols into symmetrical disulfides in high yields. Among the studied azo compounds, 4,4'-azopyridine was found to be very efficient for the odorless conversion of alkyl halides into disulfides in the presence of thiourea. An attractive feature of this azo compound is that its obtained solid side product hydrazine is easily separated by filtration and can be recycled to its azo compound for further use.
Phototropin-Inspired Chemoselective Synthesis of Unsymmetrical Disulfides: Aerobic Oxidative Heterocoupling of Thiols Using Flavin Photocatalysis
Iida, Hiroki,Katsube, Daichi,Oka, Marina,Tsuji, Takeshi
supporting information, p. 9244 - 9248 (2020/12/21)
Inspired by the photochemical mechanism of a plant blue-light receptor, a unique flavin-based photocatalytic system was developed for the chemoselective heterocoupling of two different thiols, which enabled the facile synthesis of unsymmetrical disulfides. Owing to the redox- and photo-organocatalysis of flavin, the coupling reaction took place under mild metal-free conditions and visible light irradiation with the use of air, which is recognized as the ideal green oxidant.
THIO(DI)SILANES
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Paragraph 0081; 0087, (2020/02/10)
Thio(di)silanes comprising a thiosilane of formula (A): (R1aR1bR1cCS)s(Si)XxHh (A) wherein subscript s is from 2 to 4 or a thiodisilane of formula (I): (R1aR1bR1cCS)s(R22N)(Si—Si)XxHh (I) wherein subscript s is from 1 to 6, and wherein R1a, R1b, R1c, R2, X and subscripts n, x and h are defined herein. Also compositions comprising same, methods of making and using same, intermediates useful in synthesis of same, films and materials prepared therefrom.
