Diphenyl sulfide synthesis

The direct high yield synthesis of oxaspiropentanes from almost any type of aldehyde or ketone represents a particularly useful transformation because of the high reactivity of such compounds. This approach proves to be exceptionally simple. The DMSO reaction mixture can be directly extracted with pentane or hexane, the hydrocarbon solvent removed and the product isolated by distillation or crystallization. Since diphenyl sulfide is the only by-product extracted with the oxaspiropentane, the mixture can normally be used for most further synthetic transformations. Table 2 summarizes some of the oxaspiropentanes prepared by this method. 

Human Upoxygenase Inhibition of leukotriene synthesis by oximes of diphenyl sulfides with IC50 ca 50 nM 124... 

Oxidative polymerization of aryl disulfides has been carried out under high dilution conditions for the preparation of cyclic arylene sulfides for synthesizing cyclic arylene sulfide polymers. The readily available diphenyl disulfide and dichloro disulfide with diphenyl sulfide, diphenyl ether, or p-xylene are useful monomers for the synthesis of the corresponding cyclic oligo(thio arylene)s. The reaction scheme is shown in Fig. 30 [101]. 

The synthesis of phenothiazines starting with o-amino-o -halogeno-diphenyl sulfides has been a controversial problem, inasmuch as compounds like 8 may undergo an Ulmann-type cyclization to 2,8-disubstituted phenothiazines (9), or, through a Smiles rearrangement, may give 2,7-disubstituted phenothiazines (10). 

Several examples of the alkylation of sulfur ylides are known. " " This reaction is particularly useful for the synthesis of j-alkyl diphenylsulfonium salts which cannot otherwise be prepared from diphenyl sulfide, 5-alkyl iodides and silver tetrafluoroborate, since the latter reaction usually leads to a mixture of regioisomeric sulfonium salts. Diphenylsulfonium methanide on reaction with [ C]methyl iodide allows the synthesis of [ C]isopropyl diphenyl sulfonium salt which has been used for the synthesis of [ C]-2,3-epoxysqualene (Scheme 130, entry a). This reaction unfortunately is not general... 

Wu et al. in 1988 [43], discussed the synthesis of triarylsulfonium salts by the photolysis of a diaryliodonium salt in the presence of diphenyl sulfide. They explained the reaction using an electron transfer mechanism (see below). 

A first retrosynthetic approach disconnects the C-N bond yielding a diphenyl sulfide that can remake the initial phenothiazine via cyclization (Scheme 2). Sulfides that could produce phenothiazines by cyclization can be prepared as described in Section II.B. This is a relatively general pathway that allows for the synthesis of a large number of phenothiazine derivatives. 

This disconnection step leading to the synthesis of phenothiazines from fragments 58 and 59 is shown in Scheme 30. The preparation methods based on this scheme can be found in the chemical literature as preparations of phenothiazines by diphenyl sulfide intermediates from 2-bromo- or 2-iodo-benzenethiols and chloronitroben-zenes and as a special synthesis involving dithiocarbonates. 

Tsuchida et al. [95,96] reported the synthesis of poly(thiophenylene sulfonic acid) containing up to two sulfonic acid groups per repeating unit. Polymerisation of 4-(methylsulfinyl)diphenyl sulfide in sulfuric add upon heating or in the presence of SO3 resulted in sulfonated poly(sulfonium cation), which was then converted into the corresponding sulfonated poly(phenylene sulfide). 

Thioethers. A mixture of diphenyl sulfoxide and HMPA treated with SmL in THF under N2 at 20 for 1 min, diluted with hexane, and filtered through Florisil - diphenyl sulfide. Y 94%. The method can also be used for the rapid deoxygenation of sulfones (which may be viewed as protected thioethers). E Diphenyl sulfone under the same conditions - diphenyl sulfide. Y 93%. Esters remained intact and, in some cases, sulfoxides were selectively reduced in the presence of ketones. F.e. inch formation of cyclic tert. amines from N-oxides, tert. phosphines from phosphine oxides, and distannanes from distannoxanes, s. Y. Handa et al., J. Chem. Soc. Chem. Commun. 1989, 298-9 review of synthesis and use of polysulfoxides s. V.A. Nikonov, G.V. Leplyanin, Sulfur Reports 9, 1-23 (1989). 

Anodic synthesis. A soln. of diphenyl sulfide in anhydrous acetonitrile containing LiC104 electrolyzed at 30° with Pt-foils as electrodes without anodic-cathodic... 

The synthesis and some reactions of meso-ionic 1,2-dithioM-ones (388) have been recently reported. The brown compound 388, R = R = Ph, has been prepared by several methods (i) the reaction betw i l,l,3,3-tetrabromo-l,3-diphenylacetone (PhCBrjCOCBrjPh) and potassium ethyl xanthate, (ii) the reaction between 1,3-diphenyl-propanetrione hydrate and tetraphosphorus decasulfide, (iii) 1,3-diphenylpropanetrione with hydrogen sulfide-hydrogen chloride in ethanol-chloroform yields the salt 389, R = R = Ph, X = Cl, which gives the meso-ionic I,2-dithiol-4-one with triethylamine, pyridine, or aqueous sodium bicarbonate. ... 

Chiral sulfoxides have emerged as versatile building blocks and chiral auxiliaries in the asymmetric synthesis of pharmaceutical products. The asymmetric oxidation of prochiral sulfides with chiral metal complexes has become one of the most effective routes to obtain these chiral sulfoxides.We have recently developed a new heterogeneous catalytic system (WO3-30% H2O2) which efficiently catalyzes both the asymmetric oxidation of a variety of thioethers (1) and the kinetic resolution of racemic sulfoxides (3), when used in the presence of cinchona alkaloids such as hydroquinidine 2,5-diphenyl-4,6-pyrimidinediyl diether [(DHQD)2-PYR], Optically active sulfoxides (2) are produced in high yields and with good enantioselectivities (Figure 9.3). ... 

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