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• 501-65-5 diphenyl acetylene 
• 588-59-0 stilbene 
• 882-33-7 diphenyldisulfane 
• 4351-54-6 cyclohexyl formate 
• 100-58-3 phenylmagnesium bromide 
• 84430-52-4 (C₅H₅)Fe[P(OC₆H₅)3]2Cl 
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• 831-91-4 Benzyl phenyl sulfide 
• 67274-35-5 trimethylsilane 
• 7695-69-4 bis(phenylthio)methylbenzene 
• 622-37-7 Phenyl azide 
• 41979-02-6 α-lithiobenzyl phenyl sulfide 
• 766-92-7 [(methylthio)methyl]-benzene 

Relevant academic research and scientific papers

Synthesis of vicinal bis(alkylthio) derivatives by reductive coupling of dithioacetals derived from aromatic aldehydes with low valent titanium iodide species

Reduction of dithioacetals derived from aromatic aldehydes with low valent titanium iodide species in situ formed by treatment of titanium(IV) iodide with zinc in a mixed solvent of dichloromethane and pivalonitrile at room temperature afforded coupling products, vicinal bis(alkylthio) derivatives, in good to high yields.

Hexafluoroisopropanol-Promoted Disulfidation and Diselenation of Alkyne, Alkene, and Allene

Hexafluoroisopropanol (HFIP)-promoted disulfidation and diselenation of C-C unsaturated bonds is reported. Reactions of unactivated alkyne, alkene, and allene, respectively, with disulfides or diselenides in HFIP led to desired products in good to excellent yields (up to 96percent). In contrast, other solvents, such as isopropanol and dichloroethane, could not promote the same reaction. This method revealed an example of HFIP-promoted transformations under the mild conditions, which greatly highlighted the unique reactivity of this special solvent.

Sequential one-pot addition of excess aryl-grignard reagents and electrophiles to O-alkyl thioformates

The sequential addition of aromatic Grignard reagents to O-alkyl thioformates proceeded to completion within 30s to give aryl benzylic sulfanes in good yields. This reaction may begin with the nucleophilic attack of the Grignard reagent onto the carbon atom of the O-alkyl thioformates, followed by the elimination of ROMgBr to generate aromatic thioaldehydes, which then react with a second molecule of the Grignard reagent at the sulfur atom to form arylsulfanyl benzylic Grignard reagents. To confirm the generation of aromatic thioaldehydes, the reaction between O-alkyl thioformates and phenyl Grignard reagent was carried out in the presence of cyclopentadiene. As a result, hetero-Diels-Alder adducts of the thioaldehyde and the diene were formed. The treatment of a mixture of the thioformate and phenyl Grignard reagent with iodine gave 1,2-bis(phenylsulfanyl)-1,2-diphenyl ethane as a product, which indicated the formation of arylsulfanyl benzylic Grignard reagents in the reaction mixture. When electrophiles were added to the Grignard reagents that were generated insitu, four-component coupling products, that is, O-alkyl thioformates, two molecules of Grignard reagents, and electrophiles, were obtained in moderate-to-good yields. The use of silyl chloride or allylic bromides gave the adducts within 5min, whereas the reaction with benzylic halides required more than 30min. The addition to carbonyl compounds was complete within 1min and the use of lithium bromide as an additive enhanced the yields of the four-component coupling products. Finally, oxiranes and imines also participated in the coupling reaction. Into the melting pot: The addition of excess aryl Grignard reagents and electrophiles to O-alkyl thioformates gives aryl sulfanes through four-component coupling reactions (see scheme). These reactions may involve the formation of aromatic thioaldehydes and aryl-benzylic Grignard reagents as intermediates. For addition to carbonyl compounds, the use of lithium halides as an additive enhanced the efficiency of the reaction. Copyright

Hydrothiolation of unactivated alkynes catalyzed by indium(III) bromide

Indium(III) bromide is found to catalyze efficiently the hydrothiolation of unactivated alkynes with various thiols under mild conditions to produce the corresponding dithioacetals in excellent yields. However, addition of aromatic thiols on aromatic alky

Sulfur radical cations. Kinetic and product study of the photoinduced fragmentation reactions of (phenylsulfanylalkyl)trimethylsilanes and phenylsulfanylacetic acid radical cations

Laser and steady-state photolysis, sensitized by NMQ+, of PhSCH(R)X 1-4 (R = H, Ph; X =SiMe3, CO2H) was carried out in CH3CN. The formation of 1+.-4+. was clearly shown. All radical cations undergo a fast first-order fragmentation reaction involving C-Si bond cleavage with 1+. and 2+. and C-C bond cleavage with 3+. and 4+.. The desilylation reaction of 1+. and 2+. was nucleophilically assisted, and the decarboxylation rates of 3+. and 4+. increased in the presence of H2O. A deuterium kinetic isotope effect of 2.0 was observed when H2O was replaced by D2O. Pyridines too were found to accelerate the decarboxylation rate of 3+. and 4 +.. The rate increase, however, was not a linear function of the base concentration, but a plateau was reached. A fast and reversible formation of a H-bonded complex between the radical cation and the base is suggested, which undergoes C-C bond cleavage. It is probable that the H-bond complex undergoes first a rate determining proton-coupled electron transfer forming a carboxyl radical that then loses CO2. The steady-state photolysis study showed that PhSCH3 was the exclusive product formed from 1 and 3 whereas [PhS(Ph)CH-]2 was the only product with 3 and 4.

Steady-state and laser flash photolysis study of the carbon-carbon bond fragmentation reactions of 2-arylsulfanyl alcohol radical cations

The N-methylquinolinium tetrafluoroborate (NMQ+)-sensitized photolysis of the erythro-1,2-diphenyl-2-arylsulfanylethanols 1-3 (1, aryl = phenyl; 2, aryl = 4-methylphenyl; 3, aryl = 3-chlorophenyl) has been investigated in MeCN, under laser flash and steady-state photolysis. Under laser irradiation, the formation of sulfide radical cations of 1-3, in the monomeric (λmax = 520-540 nm) and dimeric form (λmax = 720-800 nm), was observed within the laser pulse. The radical cations decayed by first-order kinetics, and under nitrogen, the formation of ArSCH .Ph (λmax = 350-360 nm) was clearly observed. This indicates that the decay of the radical cation is due to a fragmentation process involving the heterolytic C-C bond cleavage, a conclusion fully confirmed by steady-state photolysis experiments (formation of benzaldehyde and the dimer of the α-arylsulfanyl carbon radical). Whereas the fragmentation rate decreases as the C-C bond dissociation energy (BDE) increases, no rate change was observed by the replacement of OH by OD in the sulfide radical cation (kOH/kOD = 1). This suggests a transition state structure with partial C-C bond cleavage where the main effect of the OH group is the stabilization of the transition state by hydrogen bonding with the solvent. The fragmentation rate of 2-hydroxy sulfanyl radical cations turned out to be significantly slower than that of nitrogen analogues of comparable reduction potential, probably due to a more efficient overlap between the SOMO in the heteroatom and the C-C bond σ-orbital in the second case. The fragmentation rates of 1+.-3+. were found to increase by addition of a pyridine, and plots of kbase against base strength were linear, allowing calculation of the β Bronsted values, which were found to increase as the reduction potential of the radical cation decreases, β = 0.21 (3+.), 0.34 (1+.), and 0.48 (2 +.). The reactions of 1+. exhibit a deuterium kinetic isotope effect with values that increase as the base strength increases: k OH/kOD = 1.3 (pyridine), 1.9 (4-ethylpyridine), and 2.3 (4-methoxypyridine). This finding and the observation that with the above three bases the rate decreases in the order 3+. > 1+. > 2+., i.e., as the C-C BDE increases, suggest that C-C and O-H bond cleavages are concerted but not synchronous, with the role of OH bond breaking increasing as the base becomes stronger (variable transition state). It is probable that, with the much stronger base, 4-(dimethylamino)pyridine, a change to a stepwise mechanism may occur where the slow step is the formation of a radical zwitterion that then rapidly fragmentates to products.

A kinetic study of the migration of a phenyl group from sulfur to a carbon radical center: Rearrangement of the α-(phenylthio)benzyl radical

The first rate constants for the neophyl-like 1,2-phenyl migration from sulfur to a carbon-centered radical site are reported. An Arrhenius expression was determined for the neophyl-like 1,2-phenyl migration reaction of the α-(phenylthio)benzyl radical (2) to form the diphenylmethylthio radical (6) in nonane at 160-215 °C: log (k/s-1) = (10.65 ± 0.74) - (21.4 ± 1.55) /θ, θ = 2.3RT kcal/mol (errors are 1σ). The rate constants were measured in a competition between the rearrangement of 2 versus hydrogen abstraction from thiophenol in nonane. The basis rate expression for hydrogen abstraction, log (kabs/M-1 s-1) = (8.60 ± 0.02) - (6.64 ± 0.03)/θ, was determined by a competition between self-termination (kt) of 2 and abstraction (kabs) from thiophenol from 27 to 220 °C in nonane. The relative rate expression, log (kabs/kt) = 2.86 - 5.24/θ, was converted to the absolute rate expression for abstraction by use of the von Smoluchowski expression for the self-reaction of 2, log (kt1/2) = 5.74 - 1.40/θ. Experimental diffusion coefficients of benzyl phenyl sulfide in nonane were determined for comparison with calculated values for modeling the diffusion of 2. MNDO-PM3(RHF) calculations predict that the rearrangement 2 → 6 proceeds through a transitional structure, 10, rather than an intermediate. Substituted thiaspiro[2.5]octadienyl and thiiranylcarbinyl radicals are predicted to exhibit no or low (0.5 kcal/mol) barriers to C-S cleavage, respectively, suggesting that thiiranylcarbinyl radicals are candidates for picosecond radical clocks.

N-Phehylsulphimide Formation and Rearrangement in the Thermal Reaction of Phenylnitrene with Sulphides

Thermal reaction of phenyl azide (1) with thioanisole (2a), dimethyl sulphide (2b), and tetrahydrothiophen (2c) leads to the formation of 2-substituted anilines (3a-c) by Sommelet-Hauser rearrangement of the intermediate N-phenylsulphimides arising from phenylnitrene attack at the sulphur atom of (2a-c).Reaction with ethyl phenyl sulphide (2d) gives benzenesulphenanilide (8) and ethylene by cycloelimination of the resulting N-phenylsulphimide.Reaction with acyclic benzylic sulphides (2e-g) apparently leads only to the insertion products of phenylnitrene into benzylic C-H bond, presumably through Stevens rearrangement of the intermediate sulphimides, whereas Sommelet-Hauser rearrangement appears to compete favourably with Stevens rearrangement in the sulphimide resulting from reaction of phenylnitrene with the cyclic benzylic sulphide (2h).

REACTIONS OF SULFINYL CARBANIONS WITH ORGANOMETALLIC COMPOUNDS: PREPARATION OF

Sulfinyl carbanions, -Li+ (R = Ph, Me; R' = H, Ph) have been observed to have often low reactivity towards neutral transition metal organometallic systems.When reactions do occur they usually involve salt eliminations and

Sulphur Nitrides in Organic Chemistry. Part 8. Reaction of Tetrasulphur Tetranitride with Grignard Reagents and Organolithium Compounds

The reaction of tetrasulphur tetranitride (N4S4) (1) with Grignard reagents (2a-h) and organolithium compounds (10a-h) was investigated.It was found that the reaction of (1) with (2) gave the corresponding disulphides (4a-h) in good yields together with 1,5-diaryl-1,3,5,2,4-trithiadiazapenta-2,3-dienes (3a-c), bisarylamino sulphides (5a and b), ammonium thiosulphates (6a-e), and thiosulphonates (7a-d).Reaction of (1) with (10a-f), generated from benzyl sulphides, afforded diaryl disulphides (4a, b, and e) in moderate yields accompanied by trans-stilbenes (11a and b) and 1,2-bisphenylthio-1,2-diarylethanes (12a and b).Reaction of (1) with diphenyl(phenylthio)methyl-lithium (10g), gave diphenyl disulphide (4a), the tetraphenylethylene (11c), and benzophenone (13a), while reaction of sulphur with (10g) afforded 1,2-epithio-1,1,2,2-tetraphenylethane (15) in 52percent yield besides (4a), (11c), and (13c).Reaction of (1) with 9-phenylthiofluoren-9-yl-lithium (10h) gave (4a), bifluorenylidene (11d), 1,1'-bisphenylthiobifluorenyl (12c), fluorenone (13b), fluorenylideneaminosulphenamide (14).