Elucidation of the 1,3-sulfanylalcohol oxidation mechanism: an unusual identification of the disulfide of 3-sulfanylhexanol in sauternes botrytized wines.
A four-step purification method was developed to isolate a citrus odorant detected by gas chromatography-olfactometry (GC-O), which was apparently specific to Sauternes botrytized wines. A fragmentation pattern of the odorant was obtained by multidimensional gas chromatography-mass spectrometry-olfactometry (MDGC-MS-O). The exact mass measurement was used to determine its elemental formula as C(6)H(12)OS. On the basis of these data, the unusual structure of 3-propyl-1,2-oxathiolane was synthesized and characterized for the first time. This confirmed its identification. Its occurrence in Sauternes wine extracts was demonstrated to result from the thermal oxidative degradation of 3-sulfanylhexanol disulfide (3,3'-disulfanediyldihexan-1-ol) in the GC injector. This disulfide was synthesized and then firmly identified for the first time in Sauternes wine. Although the presence of 3-sulfanylhexanol oxidation products had previously been reported in natural extracts (but not wine), the full oxidation pathway from 3-sulfanylhexanol to 3-propyl-γ-sultine via 3,3'-disulfanediyldihexan-1-ol was clearly established for the first time. Because the disulfide has mainly been detected in Sauternes botrytized wines, this finding suggested a singular reactivity of 3-sulfanylhexanol in botrytized wines, thus opening up a wide range of new opportunities in wine chemistry.
Sarrazin
Elise
E
UMR INRA 1219 Œnologie, Institut des Sciences de la Vigne et du Vin, Université Victor Segalen Bordeaux II, 210 Chemin de Leysotte, CS 5008, F-33882 Villenave d'Ornon, France. elise.sarrazin@unice.fr
Shinkaruk
Svitlana
S
Pons
Monique
M
Thibon
Cecile
C
Bennetau
Bernard
B
Darriet
Philippe
P
D002849:Chromatography, Gas; D004220:Disulfides / Q000032:analysis*; D008401:Gas Chromatography-Mass Spectrometry; D000441:Hexanols / Q000032:analysis* / Q000737:chemistry; D006358:Hot Temperature; D009812:Odorants / Q000032:analysis; D010084:Oxidation-Reduction; D012903:Smell; D013438:Sulfhydryl Compounds / Q000032:analysis* / Q000737:chemistry; D014920:Wine / Q000032:analysis*
D004220:Disulfides; D000441:Hexanols; D013438:Sulfhydryl Compounds; C477019:3-mercaptohexanol