Diphenyl Sulfone Derivatives

1 chloride with -hydroxy-4-(octyloxy)benzophenone in the presence of aluminium chloride in nitrobenzene at r.t. for 24 h [1474]. 

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Tnfluoroacetic anhydnde in a mixture with sulfuric acid is an efficient reagent for the sulfonylation of aromatic compounds [44] The reaction of benzene with this system in nitromethane at room temperature gives diphenyl sulfone in 61% yield Alkyl and alkoxy benzenes under similar conditions form the corresponding diaryl sulfones in almost quantitative yield, whereas yields of sulfones from deactivated arenes such as chlorobenzene are substantially lower [44] The same reagent (tnfluoroacetic anhydride-sulfunc acid) reacts with adamantane and its derivatives with formation of isomeric adamantanols, adamantanones, and cyclic sultones [45]... 

Poly(arylene ether benzoxazole)s were also synthesized from the reaction of bis[(4-hydroxyphenyl)benzoxazole]s and activated aromatic difluoro monomers as shown in Eq. (7) [28,29]. The bis[(4-hydroxyphenyl)benzoxazole]s were readily prepared by condensation of the appropriate bis(o-aminophenol) (e.g. 3,3 -dihydroxy-4,4 -diaminobiphenyl) with phenyl-4-hydroxybenzoate in diphenyl sulfone at 260°C. Under proper conditions, the less expensive 4-hydroxybenzoic acid can be used in place of the phenyl ester to provide high yields of the desired bis[(4-hydroxyphenyl)benzoxazole]s. As presented in Table 9, the hexafluoroisopropylidene (6F) containing polymers were amorphous. These polymers were prepared in DMAc. However, the polymers derived from 6,6 -bis[2-(4-hydroxyphenyl)benzoxazole] were prepared in diphenyl sul-... 

Friedel-Crafts sulfonylation of benzene and its derivatives can also be carried out using iron(III) chloride-based ionic liquids, as was shown by Samant and coworkers [23]. For example, the synthesis of diphenyl sulfone, an important intermediate for the anti-leprosy drug Dapsone, was achieved in 78% yield catalyzed by 1-butyl-3-methylimidazolium chloride combined with FeCl3 (Scheme 6.7). 

Bis(phenoxy) and Bis(phenylthio) Sulfone Monomers Soluble aromatic polyethers were obtained by the oxidative polymerization of 4,4 -bis(phenoxy)diphenyl sulfone, of its substituted derivatives and 4,4 -bis(phenylthio)diphenyl sulfone [Eq. (65)] [210]. The solubility and yield of the polymers was increased by the presence of methyl, tert-butyl, and methoxy group substituents on the phenoxy group of 365 (Fig. 50). 

Figure 51 Mechanism of oxidative polymerization of derivatives of 4,4 -bis(phenoxy)diphenyl sulfone and 4,4 -bis(phenylthio)diphenyI sulfone. (From Ref. 210.)...

In summary, the polymerization of 4,4 -bis(phenoxy)diphenyl sulfone and its derivatives substituted with various electron-donating groups, and 4,4 -bis(phenylthio)diphenyl sulfone produced polymers of low molecular weight. The trends in the polymerizability of these monomers indicated that the nucleophilicity and oxidizability of these monomers are the most important factors [210],... 

A series of polymerizations were performed to determine the effect of changing the diphenyl sulfone central group of the bis(phenoxy) and bis(phenylthio) monomers to a pentanedioxy group. The polymers obtained from methyl-substituted 1,5-bis(phenoxy)pentane contained structural units derived from proton transfer reactions [214]. Thus diphenyl methane, 1,2-diphenyl ethane, and benzyl chloride units were detected (Fig. 52). 

By reaction with sodium dithionite, the diphenyl- and triphenylcyclopropenylium ions 5 (R = H, Ph) were transformed into the dicyclopropenyl sulfone derivatives 6, which upon photolysis were cleanly converted into tetraphenyl- or hexaphenylbenzene (8, R = H, Ph), presumably through formation of the quadricyclane-type derivative 7. ... 

All of the materials used in this study were from commercial sources with the exception of N-phenylglycine (NPG) which was synthesized (9). The SAMs used (Figure 2) were mono(2-methacryloyloxy)ethyl phthalate, MMEP, (Rhom Tech., Inc., Malden, MA), biphenyl dimethacrylate, BPDM, and diphenyl sulfone dimethacrylate, DSDM, (Bisco Inc., Itasca. IL), all derived by the reaction of 2-hydroxyethyl methacrylate with the appropriate anhydride. Adaptic (Johnson and Johnson, East Windsor, NJ) was used as the chemically activated composite restorative material. Extracted non-carious human molars, which were stored in... 

In the even more crystalline polyethers derived from the benzophenone systems rather than sulfone systems, even higher boiling solvents like diphenyl sulfone are required. Thus the polyether from hydroquinone and 4,4 -difluorobenzophenone requires diphenyl sulfone and a temperature of 300-320°C, which approaches the melting point of the polymer (335 C). 

Studies of the reaction of benzene with chlorosulfonic acid (one molar equivalent) showed that the major product was benzenesulfonic acid (Equation 21) with a little diphenyl sulfone. When an excess of chlorosulfonic acid was used benzenesulfonyl chloride was obtained (Equation 22). Spryskov and Kuz mina demonstrated the reversibility of Equation 22 and measured the equilibrium constants for several different aromatic substrates. In the benzene-chlorosulfonic acid reaction, the quantity of diphenyl sulfone produced was increased by addition of anhydrous benzenesulfonic acid, but not by benzenesulfonyl chloride. The sulfone therefore apparently derived from reaction of benzenesulfonic acid and benzene under the influence of chlorosulfonic acid. Sulfone formation appeared to be relatively favoured at low temperatures and this may be due to the formation of an intermediate pyrosulfuric acid (Equations 23,24). 

Bassin, Cremlyn and Swinboume. Details of kinetic and mechanistic studies on sulfonation and chlorosulfonation of aromatic hydrocarbons and other derivatives have been described in Chapter 2. Chlorosulfonic acid is a very active sulfonating agent and when benzene is added to an excess of the reagent at room temperature, benzenesulfonyl chloride is formed (> 70%) with only a trace of diphenyl sulfone. " On the other hand, when an excess of benzene is present, the major products are diphenyl sulfone and benzenesulfonic acid. " ... 

The cyclization of diphenyl ether 206 to the cyclic sulfone derivatives 208 and 209 achieved by prolonged heating with a large excess of the reagent is analogous to similar reactions observed with biphenyl and the diphenyl alkanes (see Section 2, pp 42 and 40). 4-Bromodiphenyl ether by treatment with excess chlorosulfonic acid (two equivalents) at 25-30 °C afforded the 4-sulfonyl chloride (45%). In this molecule, the other reactive 4-position is blocked by the bromine atom. In contrast, with diphenyl ether 206 all attempts to obtain the monosulfonyl chloride by reaction with chlorosulfonic acid failed, and the only isolated product was the 4,4 -disulfonyl chloride. In the case of 4,4 -dibromodiphenyl ether, in which... 

It was also discovered that diphenyl sulfone 223, by prolonged heating with chlorosulfonic acid (six equivalents) at 90 °C, gave a low yield of the 3-sulfonyl chloride 225 (Equation 71). Treatment of ethyl phenylsulfone and its p-chloro derivative with the reagent both yield the corresponding 3-sulfonyl chlorides so that sulfonation occurs, as expected, in the meta position relative to the sulfonyl group. Di-p-xylylsulfone reacts with chlorosulfonic acid (10 parts, 150-160 °C) to yield the 3,3 -disulfonyl chloride. ... 

Several arylsulfones are effective acaricides thus diphenyl sulfone is especially toxic to the eggs of the fruit tree spider mite and the 2,4,5-trichloro- and the 2,4,5,4 -tetrachloro derivative (tetradifon 23) are valuable acaricides. ... 

FIG. 1.9 Copol3fmer of diphenyl sulfone with phenolphthalein or with its sulfonated derivative (sDCPDS). 

Ueda et al. focused their attention on a binaphthyl structure, which has a high hydrophobicity and a large free volume derived from its twisted structure, and was expected to show a low WU even after sulfonation. The monomer, 4,4 -di (l-naphthoxy)diphenyl sulfone, was successfully prepared by a nucleophilic aromatic substitution reaction between 4,4 -dichlorodiphenyl sulfone and 1-naphthol. A highly SPES with highly hydrophobic binaphthyl units (lEC = 3.19 meq./g, BNSH-lOO(OX)) was obtained by the oxidative polymerization of 4,4 -di(l-naphthoxy) diphenyl sulfone with ferric chloride as an oxidant, followed by postsulfonation into the binaphthyl units (Scheme 4.15). 

Amination at an azole ring nitrogen is known for Af-unsubstituted azoles. Thus 4,5-diphenyl-1,2,3-triazole with hydroxylamine-O-sulfonic acid gives approximately equal amounts of the 1- (104) and 2-amino derivatives (105) (74AHC(16)33). Pyrazole affords (106) and indazole gives comparable amounts of the 1- and 2-amino derivatives. 

The 2,2 -bis(phenylthiomethyl) dispiroketal (dispoke) derivative is cleaved by oxidation to the sulfone, followed by treatment with LiN(TMS)2. The related bromo and iodo derivatives are cleaved reductively with LDBB (lithium 4,4 -di- -butylbiphenylide) or by elimination with the P4- -butylphosphazene base and acid hydrolysis of the enol ether. The 2,2-diphenyl dispiroketal is cleaved with FeCl3 (CH2CI2, rt, overnight)." The dimethyl dispiroketal is cleaved with TFA, and the allyl derivative is cleaved by ozonolysis followed by elimination. ... 

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