Bis phenylthio

Vanadium pentoxide and mercuric oxide were used as catalysts for the hydrogen peroxide oxidation of bis(phenylthio)methane to its monooxide 17a31 (equation 5). From the synthetic point of view, it is interesting to note that vanadium pentoxide, in addition to its catalytic action, functions also as an indicator in this reaction. In the presence of hydrogen peroxide, the reaction mixture is orange while in the absence of hydrogen peroxide a pale yellow colour is observed. Thus, it is possible to perform the oxidation process as a titration ensuring that an excess of oxidant is never present. 

C,3H i,N05S 149490-60-8) see Tirofiban hydrochloride rcrt-butyl P-[l,2,3,4-tetrahydro-l,l-bis(phenylthio)-2-oxo-... 

The submitters obtained 59.6-64.1 g. (65-70%) of product melting at 36-37° after recrystallization from ethanol. Reported melting points for bis(phenylthio)methane are 34-35°, 38-40°, and 39.5-40.5°." The proton magnetic resonance spectrum of the product in carbon tetrachloride exhibits a two-proton singlet at 8 4.30 and a 10-proton multiplet at 8 7.10-7.56. 

Thiophenol Benzenethiol (8, 9) (108-98-5) 4,4-Bis(phenylthio)-3-methoxy-l-butene Benzene, 1, T-[(2-meth-oxy-3-butenylidene)bis(thio)]bis- (9) (60466-65-1)... 

Unexpected transformations of 5-(phenylthio)pent-2-en-4-ynal and 5-(methylthio)pent-2-en-4-ynaI to 2-bis(phenylthio)- and 2-bis(methylthio)methylfurans respectively in the presence of a slight excess of HCl have been recorded. The transformations are expected to involve a pyran to furan ring-contraction sequence <00HCA1191>. 

Bis(pentanoyloxy)dibutylstannane [3465-74-5] Bis(p-phenoxyphenyl)diphenylstannane [17601-12-6] Bis(phenylthio)dimethylstannane [4848-63-9] Bis(phenylthio)diphenylstannane [1103-05-5] Bis(propanoyloxy)dibutylstannane [3465-73-4] Bis(tetradecanoyloxy)dibutylstannane [28660-67-5]... 

Ring-closing metathesis of [2,2-bis(phenylthio)ethyl]dimethyl-(l-phenylbut-3-enyloxy)silane (89) and subsequent oxidation [33]... 

To a solution of the titanocene(II) reagent 29 in THF (42 mL) in a 300-mL round-bottomed flask, prepared from titanocene dichloride (6.54 g, 26.3 mmol), magnesium turnings (0.766 g, 31.5 mmol), triethyl phosphite (8.96 mL, 52.5 mmol), and finely powdered 4 A molecular sieves (1.31 g) according to the procedure described above, was added a solution of l,l-bis(phenylthio)cyclobutane (63 2.29 g, 8.40 mmol) in THF (14 mL). The reaction mixture was stirred for 15 min. and then a solution of (S)-isopropyl 3-phenylpro-panethioate (91 1.46 g, 7.00 mmol) in THF (21 mL) was injected dropwise over a period of 10 min. The reaction mixture was refluxed for 1 h, then cooled, whereupon 1 m aq. NaOH solution (150 mL) was added. The insoluble materials produced were removed by filtration through Celite and washed with diethyl ether. The aqueous layer was separated and extracted with diethyl ether. The combined ethereal extracts were dried (Na2S04), filtered, and concentrated. The residual liquid was purified by column chromatography (silica gel, hexane) to afford 1.33 g (77%) of (l-isopropylthio-3-phenylpropan-1 -ylidene) cyclobutane (92). 

Bis(phenylthio)methyUithium, LiCH(SC6H5)2 (1). The reagent is obtained in high yield by reaction of bis(phenylthio)methane in THF with BuLi at 0°. ... 

Cyclopropanation of enones.1 Reaction of an enone with tris(phenylthio)-methyllithium and then with CuOTf (1 equiv.) results in a bis(phenylthio)-cyclopropane (equation I). 

Recently, a synthesis of tetrodotoxin from D-glucose was described (Scheme 36). After a Michael addition of the lithium salt of bis(phenylthio)-methane to the nitroolefin 116, the major component (117b) of the resulting epimeric mixture 117a + 117b was subjected to a reaction sequence that involved an intramolecular nitroaldol reaction, to give the complex nitro cyclohexane derivative 118. 

A rather complex mixture of products is obtained from the reaction of benzyl-idenetriphenylphosphorane and CS2.48 The major product from the reaction of diphenyl disulphide with methylenetriphenylphosphorane is tris(phenylthio)-methane (44) and only a trace of the insertion product bis(phenylthio)methane is isolated.49 Presumably the salt (45) is deprotonated before it can react with the phenylthioate anion (Scheme 12). a-Thiocarbonyl-stabilized ylides (46) are obtained from the reaction of ylides with S-alkyl thiolcarboxylates.50... 

TLC analysis (10% benzene, 90% hexanes) of the crude reaction mixture (95% yield) indicates complete conversion of vinyl bromide (Rf = 0.5) to phenylthioacetylene (Rf = 0.6). A minor product, which can be purified by flash column chromatography and identified as cis-1,2-bis(phenylthio)ethylene,5 is also detected (Rf = 0.3) in variable amounts (5-15% yield) depending on the run. 

Phenylthioacetylene has been prepared by elimination of thiophenol and dehydrobromination of cis-1,2-bis(phenylthio)ethylene5 and cis-1-bromo-2-phenylthioethylene,2 7 respectively. The latter was obtained by addition of thiophenol to propiolic acid in ethanol and subsequent one-pot bromine addition, decarboxylative dehalogenation, and careful distillation to remove the trans isomer.2.7 on the other hand, cis-1,2-bis(phenylthio)ethylene was prepared by double addition of thiophenol to cis-1,2-dichloroethylene.5a d Although these procedures can provide useful amounts of phenylthioacetylene, they were found to be somewhat less satisfactory in our hands as far as operation and/or overall yields are concerned. Furthermore, we have encountered problems with regard to the reproducibility of one-pot dehydrobrominations of phenylthio-1,2-dibromoethane.6 However, the stepwise execution of the double dehydrobromination, as described in the modified procedure reported here, provides preparatively useful quantities of phenylthioacetylene in a practical manner. 

Scheme 26 Anodic ring opening of 1, l-bis(phenylthio)-cyclopropanes.

Steele, W.V., Chirico, R.D., Cowell, A.B., Knipmeyer, S.E., and Nguyen, A. Thermodynamic properties and ideal-gas enthalpies of formation for 2-aminoisobutyric acid (2-methylalanine), acetic acid, ( -5-ethylidene-2-norbornene, mesityl oxide (4-methyl-3-penten-2-one), 4-methylpent-l-ene, 2,2 -bis(phenylthio)propane, and glycidyl phenyl ether (1,2-epoxy-3-phenox3q>ropane), / Chem. Eng. Data, 42(6) 1053-1066, 1997. 

It is not surprising that chloro esters 1, 2 readily add thiols, catalyzed by sodium thiolates or triethylamine, to give the corresponding 2-(r-organylthiocy-clopropyl)-2-chloroacetates 85,86 (Scheme 22) [15 b, 22b, 27]. This reaction with thiophenol has been used to quantify the Michael reactivity of 1-Me, 2-Me, 3-X in comparison to simple acrylates (see above). With an excess of PhSH, the nucleophilic substitution of the chlorine in 85 a (but not in 85h) proceeded to give the corresponding bis(phenylthio) derivative in 63% yield [15bj. Alkali thiolates (e.g. NaSMe, NaSBn) add smoothly onto 1-Me, 2c-Me and 2p-Me at - 78 °C, because at this temperature subsequent nucleophilic substitution of the chlorine is much slower [7l, 9]. The Michael additions of sodium phenylselenide and sodium arylsulfenates onto 1-Me and their synthetic utility have been discussed above (see Table 1). 

A new cyclic SS bond as in (147) is formed when the 3-acylimino group in 1,2-dithiacyclopentene (146) is sulfurized by 2,4-bis(phenylthio)-l,3-dithia-2,4-diphosphetane 2,4-disulfide <85CC1704>. 

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