33585-15-8Relevant articles and documents
Interpretation of the reduction potential of 6,6′-dithiosucrose cyclic disulfide by comparison of the conformations of 6,6′-dithiosucrose cyclic disulfide, 6,6′-dithiosucrose, and sucrose in aqueous solution
Lees, Watson J.,Whitesides, George M.
, p. 1860 - 1869 (1993)
6,6′-Dithiosucrose (sucrose dithiol, Suc(SH)2) is a weakly reducing species. The equilibrium constant for reduction of mercaptoethanol disulfide, MEox, by sucrose dithiol in aqueous solution is Keq = 0.3 M = {[SucS2][Mered]2}/{[Suc(SH) 2][MEox]}, where SucS2 (6,6′-dithiosucrose cyclic disulfide, sucrose disulfide) is the cyclic disulfide formed from the oxidation of sucrose dithiol. Measurements of values of T1, and J using 1H NMR spectroscopy indicate that sucrose and sucrose dithiol adopt indistinguishable conformations in water. The conformations of sucrose dithiol and sucrose disulfide are similar but distinguishable. Molecular mechanics calculations indicate that two of the possible structures of sucrose disulfide have relatively low energies. Comparison of coupling constants calculated for these structures with experimental coupling constants from 1H NMR spectra indicated that one of the two structures was more probable; this more probable structure had the conformation more similar to that of sucrose. The reduction potential of the Suc(SH)2/SucS2 (an 11-membered ring) couple is similar to that of an n-alkane-1,n-dithiol/cyclic disulfide (n = 5 or 6) couple; the value of EC (effective concentration = Keq = 0.3 M) characterizing oxidation of the two thiols of SuC(SH)2 to a disulfide is similar to that for oxidation of the two thiols of hexane-1,6-dithiol (Keq = 0.2 M) and pentane-1,5-dithiol (Keq = 3.6 M). The similarity of these values of EC suggests that SucS2 is a relatively strain-free structure and reflects the proximity of the two thiol groups in this carbohydrate.
BRIDGED DERIVATIVES OF SUCROSE: THE SYNTHESIS OF 6,6'-dithiosucrose, 6,6'-epidithiosucrose, and 6,6'-epithiosucrose
Hough, Leslie,Sinchareonkul, Lee V.,Richardson, Anthony C.,Akhtar, Farida,Drew, Michael G. B.
, p. 145 - 160 (1988)
Selective iodination and bromination of sucrose at C-6 and C-6' has been accomplished by reactions with iodine-triphenylphosphine-imidazole and carbon tetrabromide-triphenylphosphine-pyridine, respectively.Substitution of the bromo groups in 6,6'-dibromo-6,6'-dideoxysucrose hexa-acetate by CNS(1-), AcS(1-), and Me2NCS2(1-) took place without complications, but when EtOCS2K was used, a complex reaction sequence took place leading to 6,6'-epithiosucrose hexa-acetate.Similarly, reaction of the dibromo derivative with K2CS3 afforded mainly the 6,6'-episulphide together with 6,6'-epidithiosucrose hexa-acetate, which was also formed from the dibromide by sequential treatment with thiourea and sodium metabisulphite.Oxidation of the episulphide with sodium metaperiodate afforded solely the (R)-sulphoxide, and oxidation with hydrogen peroxide afforded the sulphone.The episulphide, the episulphide S,S-dioxide, and the episulphide all showed conformational instability of the ring containing the sulphur atom(s), as indicated by the n.m.r. spectra, but the episulphide S-oxide did not show this behaviour.
Library of mild and economic protocols for the selective derivatization of sucrose under microwave irradiation
Barros, M. Teresa,Petrova, Krasimira T.,Correia-Da-Silva, Paula,Potewar, Taterao M.
supporting information; experimental part, p. 1897 - 1906 (2011/09/19)
The chemistry of sucrose is very challenging due to its eight hydroxyl groups, three of which are primary, with very similar reactivities, thus control of the chemoselectivity is a central issue. In this work, the selective formation of monounsaturated es
