Sulfone derivatives

Some 5-substituted 2-aminothiazoles with alkyl (15, 173, 175, 224, 366, 396), ester (173, 184, 220), aryl (115, 265, 396, 414), a-naphthyl (463), sulfur and sulfones derivatives (329, 373), isonitrosomethyl (772), and chloro groups were synthetized from the corresponding a-haloaldehyde and thiourea in lower yield (Table 11-14). 

To overcome these difficulties, drilling fluids are treated with a variety of mud lubricants available from various suppHers. They are mostly general-purpose, low toxicity, nonfluorescent types that are blends of several anionic or nonionic surfactants and products such as glycols and glycerols, fatty acid esters, synthetic hydrocarbons, and vegetable oil derivatives. Extreme pressure lubricants containing sulfurized or sulfonated derivatives of natural fatty acid products or petroleum-base hydrocarbons can be quite toxic to marine life and are rarely used for environmental reasons. Diesel and mineral oils were once used as lubricants at levels of 3 to 10 vol % but this practice has been curtailed significantly for environmental reasons. 

An assessment of the toxicity potential of chemicals used in EOR has been reviewed (181). A series of first-intent petroleum sulfonates derived from petroleum fractions were synthesized along with a series of od-soluble synthetic sulfonates. Their properties and preliminary od recoveries have been reported (182). 

Sulfonic acids may be subjected to a variety of transformation conditions, as shown in Figure 2. Sulfonic acids can be used to produce sulfonic anhydrides by treatment with a dehydrating agent, such as thionyl chloride [7719-09-7J. This transformation is also accomphshed using phosphoms pentoxide [1314-56-3J. Sulfonic anhydrides, particulady aromatic sulfonic anhydrides, are often produced in situ during sulfonation with sulfur trioxide. Under dehydrating conditions, sulfonic acids react with substituted aromatic compounds to give sulfone derivatives. 

There are three color additives of the indigoid type, including D C Blue No. 6 (35) (an insoluble pigment), FD C Blue No. 2 (2) (the water-soluble disodium sulfonate derivative of indigo), and D C Red No. 30 (23) (an insoluble thioindigoid). AH are related to indigo [482-89-3] which has stmcture (35) (Fig. 3). 

Two of the remaining colorants on the Hst of certifiables are quinoliaes the solvent-soluble D C Yellow No. 11 (30b), and its water-soluble sulfonated derivative, D C Yellow No. 10 (30a) (Fig. 2). Both are derived from quiaaldine by condensation with phthaUc anhydride. 

A.mina.tlon. Amination describes the introduction of amino groups into aromatic molecules by reaction of ammonia or an amine with suitably substituted halogeno, hydroxy, or sulfonated derivatives by nucleophilic displacement. Although reaction and operational conditions vary, the process always involves the heating of the appropriate precursor with excess aqueous ammonia or amine under pressure. 

The following compounds have been obtained from thiete 1,1-dioxide Substituted cycloheptatrienes, benzyl o-toluenethiosulfinate, pyrazoles, - naphthothiete 1,1-dioxides, and 3-subst1tuted thietane 1,1-dioxides.It is a dienophile in Diels-Alder reactions and undergoes cycloadditions with enamines, dienamines, and ynamines. Thiete 1,1-dioxide is a source of the novel intermediate, vinylsulfene (CH2=CHCH=SQ2). which undergoes cyclo-additions to strained olefinic double bonds, reacts with phenol to give allyl sulfonate derivatives or cyclizes unimolecularly to give an unsaturated sultene. - Platinum and iron complexes of thiete 1,1-dioxide have been reported. 

Other sulfonate derivatives are obtained by the use of trifluoromethanesulfonyl hypochlorite and hypobromite (CF3SO2OQ and CF3S020Br) in reactions with petfluoroalkyl halides and their derivatives [30. These reactions lead to the corresponding trifluoromethanesulfonate derivatives of alkanes (equation 28) (Table 11). The reaction proceeds with complete retention of stereochemistry at the carbon center [30]. 

With hydroxylamine, HONH2, 4 of the 5 possible sulfonate derivatives have been prepared as anions of the following acids ... 

Heterocyclic sulfone derivatives with anti-HIV activity 97F321. 

Poly(arylene thioether)s, 363-364 Poly(arylene thioether sulfone)s, 364 Poly(aryl sulfone) derivatives, 354 Poly(p-benzamide), synthesis of, 188-189 Polybenzimidazoles (PBIs), 265 ferrocene-containing, 315 synthesis of, 313... 

Oxidation of thiophene with Fenton-like reagents produces 2-hydroxythiophene of which the 2(570 One isomer is the most stable (Eq. 1) <96JCR(S)242>. In contrast, methyltrioxorhenium (Vn) catalyzed hydrogen peroxide oxidation of thiophene and its derivatives forms first the sulfoxide and ultimately the sulfone derivatives <96107211>. Anodic oxidation of aminated dibenzothiophene produces stable radical cation salts <96BSF597>. Reduction of dihalothiophene at carbon cathodes produces the first example of an electrochemical halogen dance reaction (Eq. 2) <96JOC8074>. 

Colored forms of 5, 8 -disulfonate derivatives of 33 chelate with divalent metal ions, e.g., Ca2+, Cu2+, and Pb2+, causing blueshift.85 The order of blueshift and thermal stability of the chelated photomerocyanine is as follows Ca2+ < Cu2+ < Pb2+. 5 -Methoxy derivative of 33 also gives Ni2+ complexes. This chelation significantly stabilizes photomerocyanine, compared with the nonchelating colored form. In contrast to sulfonate derivatives, chelation of 5 -methoxy derivatives with Ni2+ causes redshift (ca. 40 nm), but their structures are not clear. 

The final ring coupling reaction is usually an O-alkylation of the sodium enolate with a methyl sulfonate-, bromo-, or chloro-butenolide in acetonitrile or an ether solvent (8.22-24). Use of the methyl sulfonate derivative is least preferred because of its poor stability (9,24). The isolated hydroxymethylene lactone can be allowed to react with the bromobutenolide using potassium carbonate in hexamethylphosphoric triamide (caution a potential carcinogen). 

Siderophores are iron-complexing compounds of low molecular weight that are synthesized by bacteria and fungi, and serve to deliver iron to the microbes. Because of their exclusive affinity and specificity for Fe3+, natural siderophores and synthetic derivatives have been exploited in the treatment of human iron-overload diseases. The most successfully used example is Desferal , which is the methane sulfonate derivative of iron-free ferrioxamine B, a linear trihydroxamate (Figure 3.2). Ferrioxamine was isolated in 1958 from the culture supernatant of Streptomyces... 

Wilkinson s catalyst has also been utilized for the hydroboration of other alkenes. Sulfone derivatives of allyl alcohol can be hydroborated with HBcat and subsequently oxidized to give the secondary rather than primary alcohol. This reactivity proves to be independent of substituents on the sulfur atom.36 Similarly, thioalkenes undergo anti-Markovnikoff addition to afford a-thioboronate esters.37 The benefits of metal-catalyzed reactions come to the fore in the hydroboration of bromoalkenes (higher yields, shorter reaction times), although the benefits were less clear for the corresponding chloroalkenes (Table 3).38,39 Dienes can be hydroborated using both rhodium and palladium catalysts [Pd(PPh3)4] reacts readily with 1,3-dienes, but cyclic dienes are more active towards [Rh4(CO)i2].40... 

Acid catalysed rearrangement of the tetrahydro 1-benzazepine sulfonamides 52 gave the 9-substituted sulfone derivatives 53 plus, in the case of 52b, the 7-substituted isomeric derivative... 

The Hurd-Mori reaction,where a tosylhydrazone is converted by thionyl chloride to the corresponding thiadiazole, involves the formation of a 1,2,3-thiadiazole-3,3-dioxide. In one example, this type of compound was isolated and subsequently deoxygenated with thiourea <1991PS175>. There have been no further reports of S-linked sulfoxide or sulfone derivatives of 1,2,3-thiadiazoles since the publication of CHEC-II(1996). 

Complexes of beryllium with 1,2-dihydroxybenzene (catechol) and its more soluble sulfonate derivatives (188, 198, 251-256) have been investigated with particular reference to their possible use as antidotes for beryllium poisoning. 

The interactions of NO with the iron-sulfur cluster moieties of several enzymes generate iron-sulfur-nitrosyl cluster compounds [156]. However, synthetic nitrosyl clusters such as Roussins black salt (RBS), Roussins red salt (RRS), Roussins red ester (RRE) and [FeNOS]4 (Fig. 5.3) are well known [129, 157] and can be synthesized easily [158-164]. For example, the RBS can be prepared by mixing FeS04 with NaN03 and (NH4)2S in aqueous solution [158]. RRE salts are generally insoluble in water, but recently the water soluble sulfonated derivative, Na2[Fe2(SCH2CH2S03)2(N0)4], has been prepared [165]. 

---