B -sultones

Only the a-olefins are sulfonated commercially to make a-olefinsulfonate (AOS). The chemistry of a-olefin sulfonation is usually described in terms of three stages. The initial sulfonation reaction involves the formation of 3-sul-tones. This initial step is so fast as to be almost instant. Reaction of the initially formed B-sultones with more S03 is competitive with sulfonation of the olefin. This side reaction produces a byproduct believed to be a cyclic pyro-sulfonate ester, i.e., a pyrosultone ... 

After a residence time of 15-20 minutes at slightly elevated temperature (35 C), the B-sultones have virtually disappeared and the D-sultones are only present at low levels. At this point where neutralisation followed by hydrolysis (see 3.3.4) is usually carried out, the product composition... 

FIG. 3 GC analysis of methyl esters of C14/C16 a-olefin sulfonate mixture. Peak assignments A, methyl 3-tetradecene sulfonate B, sultone from dehydration of tetradecane hydroxysulfonate C, methyl 3-hexadecene sulfonate D, sultone from dehydration of hexade-cane hydroxysulfonate. (Reprinted with permission from Ref. 7. Copyright 1995 by Karl Hanser Verlag.)... 

All the y-sultines were obtained as diastereomeric mixtures (ca 1 1, by NMR), and each one of y-sultines ( + )-49 and ( + )-51 (R = t-Bu) was separated into two diastereomers A and B by column chromatography. The oxidation of y-sultines (— )-49A and (+ )-49B to the corresponding optically active sultones (+ )-52A,B, which lack a chiral sulfur, may be taken as proof that the observed optical activity in the sultines is also due to the y-carbon. This result seems to exclude the intermediacy of vinylsulfene in the reaction mechanism, since its disrotatory closure would lead to racemic y-carbon in the product. 

The identity in sign and similarity in optical rotations of sultones (+)-52A,B, obtained from (—)-49A and (+)-49B, indicate that the absolute configuration of the y-carbon in both sultones as well as in both sultines is the same. In conclusion, the authors suggested113,114 that of the four possibilities shown below, y-sultines 48A-51A and 48B-51B may be assigned the (R)c-(Sf and (R)c-(Rf absolute configurations, respectively. Although initiated by mechanistic interest, this study has also resulted in a new method for selective synthesis of... 

Ulland B, et al Carcinogenicity of the industrial chemicals propylene imine and propane sultone. Nature 230 460-461, 1971... 

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

Doak, S.M., Simpson, B.J., Hunt, P.F. Stevenson, D.E. (1976) The carcinogenic response in mice to the topical application of propane sultone to the skin. Toxicology, 6, 139-154... 

Kaul, B.L. (1985) Induction of chromosomal aberrations and sister chromatid exchanges by propane sultone in human lymphocytes in vitro. Toxicol. Lett., 28, 139-142... 

Kaul, B.L. Tandon, V. (1981) Modification of the mutagenic activity of propane sultone by some phenolic antioxidants. Mutat. Res., 89, 57-61... 

Singh, C. Kaul, B.L. (1985) Caffeine potentiation of propane sultone mutagenesis in barley. Mutat. Res., 144, 239-242... 

A real breakthrough in this area came from the discovery that the direction of reaction could be totally changed by the use of a Lewis acid catalyst [5]. For instance, the reaction of a 30% excess of HFP with S03 in the presence of B(OMe)3 produces F-allyl fluorosulfate 2 instead of /1-sultone ... 

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 enzyme also catalyses the hydrolysis of various esters such as 4-nitrophenyl acetate and sultones. A number of slightly different enzymes, carbonic anhydrases A, B and C occur in different organisms. The most well characterised enzymes are the bovine and human carbonic anhydrases B, which are monomeric and contain one tightly bound zinc per 30000 molecular weight. 

Conger, B.V., and J.V. Carabia. Mutagenic effectiveness and efficiency of sodium azide versus ethyl methane-sultonate in maize Induction of somatic mutations... 

The basis for exploring heterocycles as inhibitors of HLE came from the discovery that some heterocycles, for example, sultones (12-1, Table 2.12) [174], oxazolinones (12-2) [175], or lactones (12-3) and (12-4) [176], were alternate substrates for serine proteinases. The proteinases reacted with these compounds to (a) cleave the heterocyclic ring, (b) form an intermediate acyl-enzyme and (c) then hydrolyze the acyl-enzyme by the normal catalytic mechanism to release active enzyme and the ring-opened heterocycle. 

SOS chromotest sfiA lacZ, alkaline phosphatase Benzofurans, naphtafurans, fungal toxins, MMC, NCS, MMS, EMS, DMS, DES, b-propiolactone, propane sultone, DMN, DEN, MNNG, B[a]P, 4NQO, DMSO, NaCI, Caffeine, Aspirin E. coli 50... 

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