Benzyl phenyl sulphone

The use of aprotic (and therefore totally unbuffered) media in analytical studies of sulphones may lead to wrong conclusions. The voltammetric determination of the benzyl phenyl sulphone was aimed to clearly exemplify the deactivation process in dry dimethylformamide. So, in aprotic or low acidity solvents, two main steps (equivalent to the transfer of one electron each) can be seen (Figure 6, curve 1). These two steps were shown at the potential of the cleavage (— 1.7 volt) to correspond, for acidic sulphones, to the following processes ... 

Benzyl phenyl sulphide was oxidized to benzyl phenyl sulphone quantitatively in 6h with iron phthalocyanine as catalyst. Experiments were similarly carried out with other metal phthalocyanines using phenyl and benzyl phenyl sulphides. Experiments using copper phthalocyanine, nickel phthalocyanine and no catalyst, were carried out for 24 h and the products analysed by HPLC. These results are presented in Table-1. In these experiments... 

Sulphonyl ylides usually are obtained by proton removal from a sulphone. Jarvis and Saukaitis" have found that the reaction of an a-bromo- or o-chloro-sulphone with triphenylphosphine resulted in abstraction of the halc en and formation of the sulphonyl ylide as an intermediate, which was trapped by protons from the water present. Benzyl phenyl sulphone was converted into the aa-dilithio-carbanion by treatment with n-butyl-lithium in THF-heptane," and Bosworth and M nus " have reported that a bicyclic phenylsulphone, upon treatment with n-butyl-lithium and then D2O, was converted into the ao-dideuteriosulphone, and that it was not possible to obtain the mono-deuteriosulphone by that method. Kaiser et al. have found that using sodium, lithium, or potassium amide with dimethyl sulphone or with dibenzyl sulphone resulted in formation of the aa -dicar-banion, as detected by deuteriation or by reaction with benzophenone. Amel and Marek determined the pK. s of a series of phenylphenacyl sulphones and concluded that the sulphone group provided less stabilization for the phenacylide than did a sulphonium group. The p value for substituents on the phenacyl portion was similar to that obtained for sulphonium, phosphonium, arsonium, and pyridinium phenacylides. 

Possibly also containing benzyl o-butyl phenyl sulphone. 

The rates of dehalogenation of a-bromo- and a-iodo-m-cyanobenzyl phenyl sulphones (81) in aqueous DMF by series of alkyidiphenyl- and substituted triaryl-phosphines have been studied. The reaction of optically active benzyl(methyl)-phenylphosphine with (81) proceeds with inversion of configuration at phosphorus. 

Benzyl phenyl sulphide, norbornene, cw-cyclooctene, and 4-vinyl-1-cyclohexene were obtained from Aldrich and (IS)-(-)-a-pinene from Fluka. Phenyl sulphide was prepared from benzene and sulphur chloride following the literature procedure[9]. Reference samples of sulphoxides and sulphones were prepared by oxidation of sulphides with sodium periodate[10] and hydrogen peroxide[ll] respectively. Reference samples of epoxides were made by following Kaneda et al.[ 2 procedure. Metal phthalocyanines[13] were prepared from appropriate metal salt, 1,2-dicyanobenzene with ammonium molybdate as catalyst and were characterized by elemental analysis. 

Results in Table-1 show that with iron phthalocyanine (Fe(II)Pc), manganese phthalocyanine (Mn(II)Pc) and cobalt tetrasulphonatophthalocyanine (Co(II)TSPc) as catalyst both phenyl and benzyl phenyl sulphides could be quantitatively oxidized to corresponding sulphones in 3-6 h. However, oxidation of benzyl phenyl sulphide to the corresponding sulphone with vanadyl phthalocyanine took 18h. In case of copper phthalocyanine (Cu(II)Pc) and nickel phthalocyanine (Ni(II)Pc), no sulphone formation was detected even after 24h, and the products analysis by HPLC showed the formation of 61% and 4.2% benzyl phenyl sulphoxide, respectively. The results for the oxidation of benzyl phenyl sulphide with Ni(II)Pc as catalyst and without any catalyst (entry 9, 10 Table-1) show that Ni(II)Pc rather gave negative effect in these oxidations. 

Benzyl p-tolyl-[ 0 0]sulphone, D 3.4 Phenethyl phenyl sulphone, A 13.7 (2-Hydroxymethylphenyl)-p-tolyl sulphoxide, Z 6.5... 

Deoxy-L-threose and -erythrose derivatives are available from ethyl 0-benzyl-L-lactate by chain elongation with the formyl anion eguivalent (21) and subseguent reduction of ketone (22) (Scheme 5). The anion of methyl phenyl sulphone has been added... 

Peroxybenzoic acid readily oxidizes aryl and alkyl sulphoxides in acetone, methylene chloride or chloroform solutions, to the sulphone in high yield . The reaction is second order and acid catalysed as is the reaction with peracetic acid . The rate of oxidation is about five times faster than when peracetic acid is used. Other work considering the oxidation of sulphoxides with peracids gathered kinetic evidence and showed that the reaction was indeed second order and that the reaction involved nucleophilic attack by the sulphoxide sulphur atom on the peracid moiety. A further study by the same authors showed that with benzyl and phenyl alkyl sulphoxides the rate of reaction was very sensitive to the inductive effect of the alkyl group. Support for the nucleophilic attack by the sulphur atom on the peracid in acidic solution was forthcoming from other sources . ... 

The availability of Nafion on silica has not only lowered the cost of the resin but also has made it versatile (Sun et al., 1997 Harmer et al., 1998). A number of industrially important reactions have been attempted, with considerable success, with these catalysts. Consider the Fries rearrangement of phenyl acetate to p-acetyl phenol (/t-hydroxy acetophenone). This has been accomplished by Hoelderich and co-workers (Heidekum, 1998). In the ca.se of alkylation of benzene with benzyl alcohol, Amberlyst-15 and p-toluene sulphonic acid are ineffective and Nafion on silica works well at 80 °C. 

For example, addition of the anion of phenyl ethyl sulphone to benzyl trimethylsilyl ketone gives a silyl enol ether by the pathway depicted in Figure Si6.8. 

Indanyl)-phenol 16 was obtained by reacting p-methoxy-phenyl-acetic acid ethyl ester with benzylchloride to form a-benzyl-p-methoxyphenyl ethyl acetate, saponification into the acid, conversion of the acid with thionylchloride into the chloride, cyclization to 2-p-methoxy-phenyl-l-indanone, NaBH4 reduction to 2-p-methoxyphenyl-l-indanole, dehydration with p-toluene-sulphonic acid in toluene to 2-p-methoxyphenyl-indene, catalytic hydrogenation to 2-p-methoxyphenyl-indene, and treating the ether with HBr [Eq. (5)]. 

CeHr-CHjSOsOH Phenyl methyl sulphonic acid or Benzyl sulphonic acid... 

Both of these compounds yield sulphides or thio-ethers. Thio-phenol by the diazo reaction yields di-phenyl sulphide, CeHs—S—Cell5, di-phenyl thio-ether and benzyl mercaptan yields di-benzyl sulphide, CeHs—CH2—S—CH2—CeHs, di-benzyl thio-ether. These sulphides on oxidation yield sulphones (p. 526). 

Desmocoll 176 is compatible with such plasticizers as benzyl butyl phthalate, diphenyl cresyl phosphate and trichlorethyl phosphate. It has slight or no compatibility with dibutyl phthalate, dioctyl phthalate, triphenyl phosphate, tricresyl phosphate, dibutyl adipate, benzyl octyl adipate, phenyl and cresyl alkyl sulphonates. 

Ultraviolet Spectra.—Interaction between the chromophores in phenylsulphonyl-guanidines through an empty c/-orbital on S, and between the sulphone w-system and the guanidine chromophore, is indicated by u.v. spectra, while related studies show the lack of homoconjugation (through-space conjugation) in aryl benzyl sulphides. U.v. fluorescence and phosphorescence data indicate exciton interaction between the phenyl chromophores in diphenyl sulphide. ... 

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