Stereospecific reaction of olefins with sulphur trioxide—dioxan

Abstract

SumnaryThe reaction of cis-and trans-but-2-ene with Similarly, sulphonation of cis-and tvn~-pent-Qene with sulphur trioxide-dioxan proceeds stereospecifically yield-sulphur trioside-diosan gave the corresponding 2,3ing cis-and trans-2,3-butanesultone, respectively, as pentanesultones. initial sulphonation products.SULPHONATION of -olefins with sulphur trioside has been extensively investigated,l but no stereochemical study on the reaction has been reported. We now report the stereochemistry of the initial products of the sulphonation reaction between cis-or trans-but-2-ene and sulphur trioxidedioxan.An equimolar amount of sulphur trioside-diosan (1 : 1) was added to cis-or trans-but-2-ene in chloroform to give the sultones (1) and (2); (1) 6 1-!5(q), 4.7--5,1(m), JAB 7.9, JBc 8.0, J m 6.0 Hz; (2) 6 1.5(q), 4.2-4.6(m), J a 6.8, These results indicate that the butane-2,3-sultones were produced stereospecifically from the corresponding but-2ene isomers. t

Chromyl chloride oxidations of olefins. Possible role of organometallic intermediates in the oxidations of olefins by oxo transition metal species

“…This process is essentially the microscopic reverse of the olefin-forming step in the Wittig reaction where a trigonal bipyramidal oxyphos- responding ß-sultones. 29 A platinum metallocycle (28) with the key structural feature of 21 has been characterized. 30 Returning to Scheme III, the cyclic organochromium intermediate 21 could then yield either the chlorohydrin precursor 20 (path b) or the epoxide precursor 22 (path b) by the appropriate reductive elimination process.…”

New reactive polymeric stabilizers for emulsion polymerization

“…There is little doubt that during the first step of the sulfonation with a sulfur trioxide -1,4-dioxane complex the corresponding sultone is formed [23][24][25][26] . The initial sultone formation occurs even stereospecific as it was shown with cis-and trans-but-2-ene in model experiments 24) . After the sultone formation rearrangements may occur as it was observed in reactions of cumulated and conjugated dienes with sulfur trioxide 25) .…”

Hydroxy alkane sulfonate (HAS), a new surfactant based on olefins

“…The identification of these compounds rests on several facts. First of all, evidence for the possible intermediacy of/3-sultones 1 in olefin sulfonation is accumulating in the literature (1,(10)(11)(12)(13)(14)(15)(16)(17)(18)(19). A concerted [2 ÷ 2] cycloaddition reaction constitutes an elegant explanation for the observed small differences in rate between olefins of different structure, as well as for the observed stereospecificity of the reaction (10,13).…”

“…The third important conclusion to be drawn from our findings is that ~-sultones 1 are by far the main intermediates in the falling-film sulfonation of internal olefins with gaseous SO3 under mild conditions. Evidence in favor of the involvement of such products has been accumulating in the literature {1, [10][11][12][13][14][15][16][17][18][19], but the involvement of/3-sultones has never been demonstrated for detergentrange internal olefins under these conditions to such an extent. In addition to the main/J-sultones, we always observe small quantities of alkenesulfonic acids 2 and ),sultones 3a.…”