Synthesis and X-ray structures of sulfate esters of fructose and its isopropylidene derivatives. Part 1: 2,3:4,5-di-O-isopropylidene-beta-D-fructopyranose 1-sulfate and 4,5-O-isopropylidene-beta-D-fructopyranose 1-sulfate.
2,3:4,5-Di-O-isopropylidene-beta-D-fructopyranose 1-sulfate have been synthesized by treatment of 2,3:4,5-di-O-isopropylidene-beta-D-fructopyranose with pyridine-sulfur trioxide complex. Direct hydrolysis of the isopropylidene group at C-4, C-5 gave 2,3-O-isopropylidene-beta-D-fructopyranose 1-sulfate. The crystal and molecular structures of ammonium (1a) and potassium (1b) salts of diisopropylidene derivative and ammonium (2) salt of monoisopropylidene derivative were determined by X-ray crystallography. Data for 1a and 1b were collected in 120 K and in 150 K for 2. All salts crystallized in P2(1)2(1)2(1) space group. There are three independent anions in asymmetric unit in 1b. Pyranose rings in the diisopropylidene derivative salts studied adopt 2S(0) twist boat conformation, whereas in the monoisopropylidene exists in a slightly distorted chair conformation (4C(1)). A staggered conformation is preferred by the sulfate group as indicated by values of C-(ester)-S-O(terminal) torsion angles: -173.2(4) degrees in 1a, 175.1(6) degrees in anion A of 1b, 170.8(6) degrees in anion C of 1b and 177.9(2) degrees in 2. However, strong interactions such as potassium-oxygen and H-bonds may affect the geometry: in anion B of 1b the value of the torsion angle is 139.4(6) degrees.
Popek
Tomasz
T
Faculty of Chemistry, University of Wroclaw, F. Joliot-Curie 14, PL-50-383, Poland.
Lis
Tadeusz
T
D000475:Alkenes / Q000138:chemical synthesis* / Q000737:chemistry; D018360:Crystallography, X-Ray; D004952:Esters / Q000138:chemical synthesis* / Q000737:chemistry; D005632:Fructose / Q000031:analogs & derivatives* / Q000138:chemical synthesis* / Q000737:chemistry; D006860:Hydrogen Bonding; D015394:Molecular Structure; D013431:Sulfates / Q000138:chemical synthesis* / Q000737:chemistry
C469236:4,5-di-O-isopropylidene-fructopyranose-1-sulfate; D000475:Alkenes; D004952:Esters; D013431:Sulfates; D005632:Fructose; C013658:propylene