4413-23-4

Upstream product

• 1450-31-3 Thiobenzophenon 
• 908093-98-1 diazodiphenylmethane 
• 81771-01-9 diphenyl(phenylthio)methyl-lithium 
• 88793-67-3 2,2,5,5-Tetraphenyl-2,5-dihydro-[1,3,4]thiadiazole 
• 470-35-9 tetraphenyloxirane 
• 200805-92-1 1,3-bis(benzylthio)-1,3-diphenylpropadiene 
• 81290-20-2 (trifluoromethyl)trimethylsilane 
• 4980-70-5 1,3-diphenyl-1-propyne 
• 3012-37-1 benzyl thiocyanate 
• 88793-70-8 C₂₆H₂₀S 

Downstream Products

• 19552-14-8 1,1-dioxo-tetraphenyl-1λ⁶-thiirane 
• 632-51-9 1,1,2,2-tetraphenylethylene 
• 119-61-9 benzophenone 
• 602-15-3 9,10-diphenylphenanthrene 
• 166264-70-6 (2-(4-nitrophenyl)ethene-1,1,2-triyl)tribenzene 

Relevant academic research and scientific papers

1,3-Dipolar cycloadditions of diphenyldiazomethane to thioketones: Rate measurements disclose thiones to be superdipolarophiles

1,3-Dipolar cycloadditions of diphenyldiazomethane to thioketones afford 2,5-dihydro-1,3,4-thiadiazoles 8, which rapidly lose N2. The liberated thiocarbonyl ylides 10 furnish thiiranes 9 by electrocyclic ring closure. The rate constants, measured by spectrophotometry (DMF, 40°C) for 16 cycloaliphatic and aromatic thioketones and one cyclic trithiocarbonate, stretch over five powers of 10 with fluorene-9-thione at the top and 2,2,5,5-tetramethylcyclopentanethione at the bottom. Electron-releasing substituents decrease the cycloaddition rate of thiobenzophenone; thus, the ambiphilic diphenyldiazomethane reacts as nucleophilic partner with the electrophilic thioketone. The influence of substituents and ring size on the reactivity of cycloalkanethiones, which are sterically hindered by two gem-dimethyl groups, will be discussed. Compared with electron-deficient C=C and C≡C bonds, thiones are superdipolarophiles.

Fluoride-assisted trifluoromethylation of aromatic thiones with (trifluoromethyl)trimethylsilane

In the presence of a stoichiometric amount of Bu4NF·3H2O, (trifluoromethyl)trimethylsilane reacts with aromatic thiones in both thiophilic and carbophilic ways to deliver, in medium yield, a mixture of (trifluoromethylthio)diarylmethane and 1,1-diaryl-2,2,2-trifluoroethanethiol, the former product being the major one.

Studies on reactions of thioketones with trimethyl(trifluoromethyl)silane catalyzed by fluoride ions

Treatment of 2,2,4,4-tetramethylcyclobutane-1,3-dione (6) in THF with CF3SiMe3 in the presence of tetrabutylammonium fluoride (TBAF) yielded the corresponding 3-(trifluoromethyl)-3-[(trimethylsilyl)oxy]cyclobutanone 7 (Scheme 1) via nucleophilic addition of a CF3- anion at the C=O group and subsequent silylation of the alcoholate. Under similar conditions, the 'monothione' 1 reacted to give thietane derivative 8 (Scheme 2), whereas in the case of 'dithione' 2 only the dispirodithietane 9, the dimer of 2, was formed (Scheme 3). A conceivable mechanism for the formation of 8 is the ring opening of the primarily formed CF3 adduct A followed by ring closure via the S-atom (Scheme 2). In the case of thiobenzophenones 4, complex mixtures of products were obtained including diarylmethyl trifluoromethyl sulfide 10 and 1,1-diaryl-2,2-difluoroethene 11 (Scheme 4). Obviously, competing thiophilic and carbophilic addition of the CF3- anion took place. The reaction with 9H-fluorene-9-thione (5) yielded only 9,9′-bifluorenylidene (14; Scheme 6); this product was also formed when 5 was treated with TBAF alone. Treatment of 4a with TBAF in THF gave dibenzhydryl disulfide (15; Scheme 7), whereas, under similar conditions, 1 yielded the 3-oxopentanedithioate 17 (Scheme 9). The reaction of dithione 2 with TBAF led to the isomeric dithiolactone 16 (Scheme 8), and 3 was transformed into 1,2,4-trithiolane 18 (Scheme 10).

Preparation and reactivity of 1,3-bis(alkylthio)allenes and tetrathiacyclic bisallenes

Reactions of Ph2C3 dianion, prepared from 1,3-diphenylpropyne and n- butyllithium, with alkyl thiocyanates or alkane dithiocyanates gave 1,3- bis(alkylthio)allenes 1 or tetrathiacyclic bisallenes 2, respectively. Thermal reactions of 1 gave thiophenes 4 and 7, benzothiepin 5, 1,2- bis(benzylidene)cyclobutane 6, thiete 8, and α,β-unsaturated ketone 9, and the reactions of tetrathiacyclic bisallenes 2a gave a cyclic dimer, 1,2- bis(benzylidene)cyclobutane derivative 10, quantitatively. Irradiation of 1,3-bis(alkylthio)allenes 1 and tetrathiacyclic bisallenes 2a caused rearrangement to give alkynes 18, 20, and 21. In the irradiation of the cyclic bisallenes 2a, isomerizations from dl to meso and meso to dl isomers were also found. In the reactions of allenes 1 and cyclic bisallenes 2a with diphenyl diazomethane, the diazomethane reacted selectively with the double bond rather than with the sulfur atom.

Reaction of thiobenzophenones with norbornadiene: unusual formation of a seven-membered cyclic sulfide

Reaction of thiobenzophenone with 2,5-norbornadiene afforded an unusual seven-membered cyclic sulfide whereas 4,4′-dimethoxythiobenzophenone reacted with 2,5-norbornadiene to afford the corresponding quinone derivative via [4+2] type cycloaddition reaction. The mechanisms of these reactions are discussed.

Nickel(0)-induced geminal bond cleavages leading to carbon-carbon double bonds: Intermediacy of nickel(0)-carbene complexes as a unifying hypothesis

The possibility of effecting geminal bond cleavages of organic monomers with nickel(0) complexes to achieve olefinic dimers has been investigated both in stoichiometric reactions between monomers of the type R2CE2 and R2C=E and the complexes (Cod)2Ni, (Et3P)4Ni and (Bpy)(Cod)Ni and in nickel(0)-catalytic α-elimination reactions of α-lithioorganic sulfones, RR′C(Li)(SO2R″). Substrates for the stoichiometric geminal bond cleavages comprised geminal dihalides, aminomethyl sulfides, cyclopropenes, thioketones and ketones. Reductive dimerization to the olefin or its hydroxy derivatives was found to occur to a varying degree in most cases, including the catalytic decomposition of the α-lithioorganic sulfones. Accordingly, this method offers considerable promise in organic synthesis. A gamut of known nickel(0) chemistry, results of chemical-trapping and spectroscopic evidence are marshaled in support of the proposal that such geminal bond cleavages and reductive coupling processes most likely proceed via nickel(0)-carbene intermediates of the type R2C=Ni · Ln.

THIONES AS SUPERDIPOLAROPHILES

According to kinetic measurements,the 1,3-cycloadditions of diphenyl-diazomethane to thioketones are much faster than those to α,β-unsaturated carbonyl compounds and nitriles previously regarded as record dipolarophiles.The primary cycloadducts are tetrasubstituted 1,3,4-thiadiazolines which extrude N2 and furnish thiiranes via thiocarbonyl ylides.

NEW THIOCARBONYL YLIDES FROM THIOBENZOPHENONE

Thiobenzophenone is converted to 1,3,4-thiadiazolines by reaction with diazoethane, phenyldiazomethane or diphenyldiazomethane at -78 deg C.Extrusion of nitrogen from the thiadiazolines furnishes thiocarbonyl ylides which, in turn, undergo electrocyclic r

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).