Alkyl sultones

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]... 

AOS is a complex mixture of different chemical species. A typical product composition is as follows [1-7] sodium alkenesulfonate (60-70%) sodium hydroxyalkanesulfonate (30%) sodium disulfonate (0-10%) 6- or 1, 4-sultone (50 ppm) unsulfonated matter (less than 2%) and inorganic salt (mainly sodium sulfate, less than 2.5%). AOS can therefore be regarded as a surfactant system in contrast with other common surfactants such as alkyl sulfates, alkyle-thoxy sulfates, alkanesulfonates, and alkylbenzenesulfonates, which consist of mixtures of their isomers and/or homologs. 

The preparation and identification of four types of S03-sulfonated products of linear and branched 1-alkenes (C5-C14) are described by Boyer [121]. 13C-and, to a lesser extent, -NMR spectra were used to ascertain the structures of 2-alkenesulfonic acids, p-sultones (as 2-methoxyalkanesulfonic acids), y- and 5-sultones. The mass spectra of some methyl 2-methoxyalkanesulfonates and 4-alkyl-5-sultones were also studied. Sufficiently volatile mixtures were separated by GLC after methylation of the sulfonic groups. 

The desulfiirisation of sultones results in the formation of an exocyclic alkene and can be achieved by an alkylation - elimination procedure <96TL 1841>. 

Sultones are useful starting materials for the preparation of various sulfoalkyl- (18, 20) or sulfoarylphosphines (7) when reacted with the appropriate alkali metal phosphide [20]. Reaction of the homologous alkyl-1,2-sultones (C3 to Cu) with tris(2-pyridylphosphine) afforded highly water soluble betains (30) [21]. 

Sultines can be versatile synthetic intermediates for example, they undergo ring-opening reactions, alkylation, reductive desulfurization , and oxidation at sulfur to give sultones. 

The interaction of sulfur trioxide with polyfluorinated vinyl ethers proceeds without a catalyst at low temperature to give /f-sultones. At higher temperature, sultones readily rearrange into the more stable acyl fluoride 91 or alkyl F-alkyl-/3-ketosulfonates. 92,93a-b [181] ... 

The same authors also report on the reaction of alkenes with chlorosulfuric acid in the absence of dioxane <1999EJ091 >. Thus, treatment of various alkenes at —40°C with chlorosulfuric acid results in the formation of, r-alkyl hydrogen sulfates (Scheme 16). From the results presented it appears that the rcr-alkyl hydrogen sulfates are transformed into a mixture of internal trans- and m-/3-sultones upon warming to 0 °C. Subsequent sulfonation of these alkenes by S03 then yields the corresponding /3-sultones. Again isolation yields were not reported but the reactions appear to proceed in a quantitative manner. The same paper also describes the use of acetyl sulfate and trifluoroacetyl sulfate for the preparation of /3-sultones, but mixtures appear to result. 

In the former product, the SO3 has added across the unsaturation in the carbon chain, resulting in a saturated alkyl chain, with an internal hydroxyl and sulphonate and a terminal carboxylate. This mechanism probably proceeds via a sultone intermediate, with the final... 

Analogous to the betaine surfactants are the sultaines and hydroxysultaines. Both are derived from either alkyl dimethylamine or alkylamidopropyl dimethylamine. Rather than being the reaction product of sodium chloroacetate, they are manufactured from a tertiary amine and either propane sultone or sodium propanechlorohydrin sulfonate (CHPS). 

With one important exception, dioxoles and oxathioles do not appear to be a particularly toxic class of compounds. The exception is 1,2-oxathiolane 2,2-dioxide (propane sultone) which produces brain tumors, leukaemias and adenocarcinomas of the small intestine in rats treated with 28 mg kg-1 orally twice a week for 60 weeks. If the toxicity is associated with its ability to act as an alkylating agent, then higher homologs should have similar, but reduced, carcinogenic potential. 

Under microwave irradiation, carbazole reacted remarkably fast with a number of alkyl halides to give Af-alkyl derivatives of carbazole (82) (Bogdal et al., 1997). The reaction was carried out with high yields by simply mixing carbazole with an alkyl halide, which was adsorbed on potassium carbonate. A facile synthesis of a series of A-alkylpyrrolidino fullerenes (83) by phase transfer catalysis without solvent under microwave irradiation has been described by De la Cruz et al. (1998), while Adamczyk and Rege (1998) have illustrated the dramatic rate acceleration for A-sulfopropylation of heterocyclic compounds using 1,3-propane sultone under microwave irradiation affording the A-sulfopropylated compounds in 68-95% yield. 

Synthesis o/eslra-l,3,5(10)-(rieiie-17-oii . Nicolaou and Barnette report that sultone 1 is metalated with KH in DME to afford a clear yellow solution of the anion 2. Alkylation of 2 with tosylate 3 followed by acid hydrolysis affords 4 as a mixture of diastereomers in 77% yield. Thermolysis of 4 affords estra-1,3,5(10)-triene-17-one (5) directly in 85% yield, probably by way of an intermediate o-quinone methide a. This sequence constitutes an exceedingly short and efficient synthesis of the steroid nucleus. 

Polysulfobetaines derived from alternating styrene-maleic anhydride copolymers 32 are easily prepared by ring opening of the anhydride moiety with 3-dimethylaminopropylamine, imidizing the resulting poly(amic acid) by heating, and alkylation with propane sultone [70-72]. For investigations of structure-property relationships additionally to 32b, the polymers 33 and 34 were synthesized [71]. The ionene-like polymer 33 was prepared... 

Sulfobutylether P-cyclodextrin is prepared by alkylation of P-cyclodextrin using 1,4-butane sultone under basic conditions. The degree of substitution in P-cyclodextrin is controlled by the stoichiometric ratio of P-cyclodextrin to sultone used in the process. 

Sultones have been shown to alkylate arenes in the presence of AICI3 (equation 70)to give aryl-alkenesulfonates. 

Reactions between SO3 and a variety of complexes " " containing the functionalized alkyl —CH2—CsC—R yield metal-sultone complexes. 

P-Lactams 28 were obtained from reaction of acylhydrazones with chloroacetyl chloride . A -Alkylation of acridine derivatives with 1,3-propane sultone gave 29. P-Phenethylamides gave 3,4-dihydroisoquinolines and N-sulfonyl gave isoquinolines 30. Nucleophilic substitution of 4-bromoisoquinoline gave the corresponding 4-substituted isoquinolines. o-Bromobenzaldehyde was reacted with allylamine and then homophthalic anhydride to afford 31. ... 

These compounds are prepared starting from chloroace-tic acid or its ethyl ester. For chains longer than acetic, cya-noethylation and hydrolysis of the nitrile obtained leads to the propionic chain, alkylation with ethyl 4-bromobutyrate and saponification leads to the butyric chain. The propane-sulfonic chains are particularly accessible by means of ring opening of propane-sultone. 

Roberts, D.W. and Williams, D.L. (1982) The derivation of quantitative correlations between skin sensitisation and physico-chemical parameters for alkylating agents and their application to experimental data for sultones. f Theor. Biol, 99, 807-825. 

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