Divinyl sulphone

Dithiolane oxides, synthesis of 241 Dithiolanes, asymmetric oxidation of 291 Divinyl sulphones, reactions of 642, 1021 Divinyl sulphoxides reactions of 349, 352, 353, 359 synthesis of 240 Donor-acceptor capacities 387... 

A surprising exception has been reported with evidence for a cleavage reaction in the case of divinyl sulphone. In non-aqueous and slightly acidic media, the behaviour of a., ji-unsaturated aromatic sulphones is also complex (see Table 7) since the cleavage and the saturation may compete. Strongly electrophilic double bonds undergo Michael additions in aprotic solvents by slowly protonated anions. Transfer of labile hydrogen may also lead to unactivated bases. It is noteworthy that in numerous cases (Table 6) the saturation is the preferred route. 

This reaction is similar of course to the corresponding elimination of hydrogen chloride from H sulphone9 to give divinyl sulphone ... 

Although an unstable triazoline intermediate was a possibility, it was thought that a concerted mechanism involving a species such as 283 was more likely When benzenesulphonyl azide was heated at 100° for 1 hr with maleic anhydride, iV -phenylmaleimide, divinyl sulphone, mesityl oxide, cyclohexene, cyclopentene, styrene, vinyl acetate or / -quinone, no gas evolution was observed, nor was there any change in the concentration of sulphonyl azide (as indicated by infrared measurement)... 

Porath, J., Laas, T., Janson, J.-Ch. Agar derivates for chromatography, electrophoresis and gel-bound enzymes - III. Rigid agarose gels cross-linked with divinyl sulphone (DVS), /. Chromatogr., 1975, 103, 49-62. 

Divinyl sulphone is also a useful cross-linking reagent ... 

The reaction of the complex (157) with divinyl sulphone gave the dihydro-thiepin 1,1-dioxide (159) instead of the expected triene (158) the latter is probably the primary product, and is converted into (159) by an intramolecular Diels-Alder reaction and subsequent isomerizations/° ... 

If butadiene is used as a coagent, the dose for gel formation is reduced by a factor 5 [77]. It is of interest that parallel to an increase of radiation yield of crosslinking, the yield of chain sdssions inoeases, as well. For instance, for butadiene, G of cross-linking is 0.69 andG of sdsdtms isO.44 for divinyl sulphone (CH, = CHSO CH=CHj) this value is 0.46 and 1.1, respectively. From the G value it may thus be seen that the... 

Figure 3. Values of In in different gels at 25° C plotted against In values in Sephadex G-15. See text for discussion. The G-numbers refer to Sephadex gels, DVS-10 is a divinyl sulphone cross-linked dextran gel (water regain = 0.99) and P-2 is polyacrylamide Biogel P-2 (water regain = 1.8).

Thebaine acts as diene component in Diels-Alder reactions with methyl vinyl sulphone or divinyl sulphone. 1 1 Adducts are formed in both cases. The analgesic properties of some elaboration products of these adducts, e.g. (136), equal the potency of codeine. Cyclopentadiene adds... 

Michael reaction. 2-Mercaptobenzothiazole undergoes the Michael addition with activated unsaturated compounds such as methyl vinyl ketone, 2- (or 4-) vinylpyridine, divinyl sulphone, and 2-nitrobut-l-ene yielding N-substituted benzothiazoline-2-thiones [e.g. (70) or (71)]. The... 

PM with divinyl sulphone allowed for enhanced retention of the encapsulated dye without compromising the loading capacity (Figure 4.13). ... 

Selenium Derivatives.—Pyrolysis of 1,2,3-selenadiazoles at 500-600 °C gives 2,4-bis(methylene)-l,3-diselenetans. Treatment of divinyl sulphone with selenium tetrabromide gave a compound that was claimed to be (125). ... 

Radial distributiQns of divinyl sulphone. The solid lines were computed for models A and B which differ in the conformational properties as well as in geometrical and vibrational parameters (see text)... 

Semiempirical CliIDO/2 calculations (Pople and Beveridge, 1970) have been seen to produce erroneous results for delocalized systems, whereas they have been proved to be useful for numerous localized systems (see e.g. Gropen and Seip, 1971 Perahia and Pullman, 1973 Corosine, Crasnier, Labarre, Labarre and Leibovici, 1973) bond lengths determined by electron diffraction for divinyl sulphone did not indicate any appreciable delocalization. 

Some of the possible rotational forms of divinyl sulphone. The three forms are characterized by the following angles of rotation ... 

Isoenergy curves calculated by the CNDO/2 method for different combinations of the angles of rotation in divinyl sulphone... 

This phenomenon has, in fact, been utilized in several structure analyses, e.g. those on chlorosulphuric acid methyl ester (Hargittai, Schultz and Kolonits, 1977) divinyl sulphone (Hargittai, Rozsondai, Nagel, Bulcke, Robinet and Labarre, 1977)> sulphonyl chloride isocyanate (Brunvoll, Hargittai and Seip,... 

Table 38 contains lengths of vinyl 0=C bonds in a series of derivatives. The G=C bonds of divinyl sulphone are of the same length, within experimental error, as that in ethylene. The G=C bond of vinyl sulphonyl chloride is among the longest, but unfortunately poorly determined. As noted by Yokozeki and Bauer (1975) the G=G bonds in substituted derivatives are longer than in ethylene, except in fluorinated compounds. The exception from the exceptions is ... 

A final example, for gas-liquid comparison with considerable differences is quoted from the infrared study of Bulcke (1975) on divinyl sulphone... 

Groups other than carbonyl can, of course, activate double bonds towards electrophilic attack consequently, divinyl sulphone reacts with pyridine in the presence of hydrochloric acid o give (76). 

The reaction of 2,3-diphenylthiiren 1,1-dioxide (8) with enamines derived from cyclic ketones gives rise to ring-enlargement products such as (9), which contain the divinyl sulphone unit e.g. the reaction of l-(l-cyclohexen-l-yl)-pyrrolidine (10) with the above thiiren gave (9 n = 1), in 86% yield. The ten-and thirteen- to fifteen-membered-ring analogues were also prepared from the... 

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