Differentiation of extractive and synthetic salicin. The 2H aromatic pattern of natural 2-hydroxybenzyl alcohol.
The natural abundance deuterium NMR characterization of four commercially available samples (Kahlbaum, Aldrich, Fluka, and Extrasynthese) of salicin 1 in comparison with two extractive samples from Salix humboldiana and Salix purpurea L. and with a synthetic material, performed on the pentaacetate derivative 2 and on diacetyl salicyl alcohol 4, is reported. Product 2 from S. humboldiana and the sample from salicin Kahlbaum show mean (D/H)aromatic values of 117 and 121 ppm, whereas, for the remaining, values of 146, 154, 153, and 150 ppm are observed, thus suggesting that salicin Kahlbaum is from extractive origin. The (D/H) values at positions 5' and 6' of the sugar moiety suggest a hypothesis on the origin of the glucose residue discriminating between those deriving from C3 or C4 plants. The analysis of 4, obtained from 3, formed in the beta-glucosidase hydrolysis of salicin 1, reveals in the natural samples from S. purpurea and from Kahlbaum the trend (D/H)4(para) > (DH)3(meta) approximately (D/H)5(meta) > (D/H)6(ortho), the first example of deuterium pattern of an ortho-oxygen-substituted phenylpropanoid. The three samples derived from commercial 1 (Aldrich, Fluka, and Extrasynthese) and the synthetic sample show almost identical deuterium content at positions 4 and 6 (around 153 ppm), whereas for the two meta positions (D/H)3 > (D/H)5 (ca. 162 and 140 ppm, respectively). Product 4, obtained from 3 submitted to acid-catalyzed deuteration, shows different deuterium incorporations in the two meta positions (which are ortho/para to the activating phenolic hydroxyl group), suggesting that possibly the deuterium abundance at the two meta positions may be affected by exchange phenomena with the medium.
Brenna
Elisabetta
E
Dipartimento di Chimica, Materiali e Ingegneria Chimica Giulio Natta, Politecnico di Milano, Milan, Italy.
Fronza
Giovanni
G
Fuganti
Claudio
C
Gatti
Francesco G
FG
Pinciroli
Matteo
M
Serra
Stefano
S
D000107:Acetylation; D000438:Alcohols / Q000737:chemistry; D001592:Benzyl Alcohols / Q000737:chemistry*; D003903:Deuterium; D005960:Glucosides; D009682:Magnetic Resonance Spectroscopy; D009812:Odorants / Q000032:analysis*; D032108:Salix / Q000737:chemistry
D000438:Alcohols; D001592:Benzyl Alcohols; D005960:Glucosides; C005696:salicin; D003903:Deuterium