Biphenyl derivatives, sulfonation

The benzene derivatives containing the fluorinated sulfone have been prepared either by nucleophilic substitution of the 4-fluorophenyl derivative (e.g. 1) or by starting with the appropriately substituted sodium thiophenoxide and reacting with perfluoroalkyl iodide follow by oxidation with either MCPBA or chromium oxide (12. li.) The biphenyl derivatives have been prepared by palladium catalyzed cross coupling chemistry of the 4-bromophenyl derivative (e.g. 2) with substituted phenyl boronic acid (yields 37-84%) (JLH, .). Compound 16 has been prepared by palladium catalyzed cross coupling of (4-bromophenyl)perfluorohexyl sulfone with vinyl anisole in 37 % yield (JJL). The vinyl sulfones, 7 and 9, have been prepared by condensation of CH3S02Rf (JJL) with the appropriate aldehyde (yields 70,and 73%) following a literature procedure (1 ). Yields were not optimized. 

Besides the TPPTS-system a number of other sulfonated phosphine ligand systems were investigated and tested on a pilot plant scale. Among them are systems which are derived from biphenyl (BISBIS = sulfonated bis(diphenylphosphinomethyl)biphenyl, varying grades of snlfonation of... 

Biphenyl and Derivatives (Table VII). Biphenyl-4-sulfonic acid can be prepared very satisfactorily by sulfonation with sulfuric acid in nitrobenzene solution (90% yield) or by the action of chlorosulfonic acid in tetrachloroethane at 50°." Sulfuric acid alone either gives a mixture of the 4-mono- and 4,4 -di-sulfonic adds with unchanged hydrocarbon or, with excess reagent, yields chiefly the di- derivative. The monosulfonic acid is readily freed from the disulfonic acid through its sparingly soluble copper salt the disulfonic acid remains in solution and can be crs stallized... 

Several carbon-hydrogen bond substitutions are involved in the palladium-catalysed reaction of arylsulfonic acids with arenes to yield aromatic sulfones. A plausible mechanism, shown in Scheme 9, involves the initial formation of the palladacycle (99) which, after eoupling with the arene, yields the biphenyl derivative (100). Further coordination and carbon-hydrogen activation gives the seven-membered palladacycle (101) that affords the sulfone, (102), after reductive elimination. ... 

Rhodococcus sp. Strain T09 A Rhodococcus strain T09 was isolated by enrichment on media-containing BT. The desulfurization mechanism of this organism was reported to be similar to Gordonia sp. 213E due to the observation of similar intermediates however, the substrate specificity was different. The strain T09 could use 2-methyl, 3-methyl and 5-methyl BT apart from BT as sole source of sulfur for growth, but not 7-methyl or ethyl derivatives. Additionally, it could also use methyl thiobenzothiazole, marcaptobenzothiazole, as well as benzene sulfide, benzene sulfonate, biphenyl sulfinate, dimethyl sulfate, dimethyl sulfone, dimethyl sulfide, methane sulfonic acid, thiophene, and taurine as sole sulfur sources. However, it could not grow on DBT or DBT sulfone. 

The Friedel-Crafts cyclization of biphenyl-2-sulfonyl chloride to give dibenzothiophene sulfone has been described (55%) ° however, thermal cyclization in octachloronaphthalene at 250°, under nitrogen, is reported to yield dibenzothiophene itself rather than the sulfone (47%). Reaction of biphenyl compounds with oleum (H2SO4 + SO3) to yield derivatives of dibenzothiophene 5,5-dioxide is widely used for the preparation of dyestuff intermediates (Section VI, E, 2). A typical example is shown in Eq. (3), starting from o-tolidine. ... 

The 3,7-disulfonyl chloride of dibenzothiophene 5,5-dioxide has been isolated from the reaction of biphenyl with chlorosulfonic acid. The reaction proceeds via the 2,4,4 -trisulfonyl chloride of biphenyl. This reaction has now been extended to give sulfonic acid derivatives of 3-phenyl- and 3-biphenylyldibenzothiophene 5,5-dioxide. Treatment of p-terphenyl with oleum or chlorosulfonic acid at 100° yields (141a) (46%), and similarly p-quaterphenyl yields 141b (47%). A later... 

Since the publication of CHEC-II(1996), there have been very few examples related to the reactivity of substituents attached to ring carbon atoms. One case involves the reaction of 3-benzylidene-2,3-dihydro-2-methyl-l,2-benzothiazin-4-one 1,1-dioxide 163 with the alkylidenephosphorane derived from salt 164 forming the tricyclic-fused ring compound 165 (Scheme 20) <1996J(P1)2541>. This material 165 was oxidized with 2,3-dichloro-5,6-dicyano-l,4-benzoquinone (DDQ) affording the biphenyl 166. Ring-opened product 167 was produced from 165 upon exposure to />-toluene-sulfonic acid and heat. 

Potent inhibition of the herpes simplex virus has been observed using biphenyl disulfonic acid urea copolymers. Sulfonic acid derivatives have been shown to be potent antihuman immunodeficiency virus (anti-HIV) agents. 

Meyer32 has shown that 2-(stilben-4-yl)- and 7-styrylbenzo[h]furans containing sulfonic acid groups can be prepared from the phenyl-iminomethyl derivatives of benzene, biphenyl, and naphthalene. 

We have found that use of fluorinated sulfone and SSI acceptors leads to materials with better nonlinearity for their transparency compared with materials containing the conventional acceptors. Figure 3 summarizes our findings, and is a plot of jlp vs Xmax for donor-acceptor CT molecules of benzene, styrene, biphenyl, fluorene, and stil-bene derivatives with fluorinted sulfone, SSI, and other common acceptors (SC>2Me, CN, COH, COMe, and NO2) groups. 

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... 

Sulfonated polyimides (sPI) are another type of ionomers that have been prepared [5] by copolymerization of 4,4 -diamino-biphenyl 2,2 -disulphonic acid (BDSA), 4,4 -oxydianiline (ODA), and naphtalenic or phthalic anhydrides. Polyimide structures based on six-membered rings derived from naphtalenics anhydrides, such as 1,4,5,8-naphtalene tetracarboxylic dianhydride (NTDA), shown in Fig. 6.8, are more hydrolitically stable than the five-membered rings basedoxy-diphthalic anhydrides (ODPA). 

Di-(styryl)-biphenyls are also obtained by the Homer-Wittig reaction of the phosphonate derived from l,4-bis-(chloromethyl)-biphenyl (37) and triethyl phosphite (38) with benzaldehyde-2-sulfonic acid (40), giving the corresponding distyrylbiphenyl disodium salt (e.g., 41, see Scheme 28.2). This class of FWAs is widely used in detergent applications due to its unique whitening benefits... 

Furans and benzo[b]furans are further building blocks of FWAs. They are used, for example, in combination with benzimidazoles and benzo[b]furans as biphenyl end groups. The 4,4 -bis (benzo[b]furan-2-yl)biphenyls can be regarded as distyrylbiphenyls that have their rings closed and are thus fixed in the Zi-confignration. Sulfonated derivatives are readily water-soluble and are used as lightfast brighteners for polyamides and cellulosic fibers. ... 

The Fenton-type system, Fe(II)/Cu(n)/H202, produced phenol with a moderate selectivity [28b]. In the absence of Cu(II) or Fe(III), biphenyl was the main product. Quinones, in particular l,2-naphthoquinone-4-sulfonate, played a vital role in the Fe(III)-promoted hydroxylation of benzene with HjOj, giving moderate yields of phenol [70]. The addition of polyethyleneglycol to Fe(III)/ HjOj in aqueous acetonitrile enhanced the phenol yield and selectivity [71]. A heterophase reaction in the presence of surfactants (quaternary ammonium salts, crown ethers, and polymers) has led to a further improvement. Biphasic benzene hydroxylation in the system composed of aqueous H O, Fe SO modified with 2-pyrazinecarboxylic acid (Hpca) derivatives, and CF COOH produced phenol with a selectivity of 97% (based on benzene) at substrate conversion of 8.6% (Eq. 14.22)... 

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