Synthesis of stable isotope labeled 3-acetyldeoxynivalenol

Abstract

Stable isotope labeled 3-acetyldeoxynivalenol (3-AcDON) was synthesized in excellent yield from deoxynivalenol as starting material. This is the first synthesis of a stable isotope labeled type-B trichothecene suitable as internal standard for HPLC-MS/MS or GC-MS analysis of trichothecene mycotoxins. The isotopic purity of the 3-d(3)-AcDON was determined to be 94.9%.

Stable isotope dilution analysis of the Fusarium mycotoxins deoxynivalenol and 3‐acetyldeoxynivalenol

“…5a). With one 13 C incorporated, the statistical distribution of it would mean a 14/15 (= 93.3%) likeliness, that it is located in the rings and a 1/15 (= 6.7%) likeliness of it being located in the neopentyl moiety at C 15 (Fig. 5b) Fig.…”

“…Furthermore, 3-AcDON is quantified with 3-d 3 -acetyldeoxynivalenol (3-d 3 -AcDON 4, Fig. 2) as isotopically labeled standard, of which the synthesis was recently published [15].…”

Synthesis of Isotope‐Labeled Deoxynivalenol‐15‐O‐Glycosides

“…For glycosylation at the 15‐position, 3‐acetyldeoxynivalenol (3‐ADON, 3 ), was used as the starting material; the second free OH group at the 7‐position is known to be biochemically and chemically inert , , . Bearing in mind the previously reported procedures for the glycosylation of DON, we tested Königs–Knorr conditions [acetobromo‐α‐ d ‐glucose ( 4 ), Ag 2 O, MeCN] to synthesize DON‐15‐ O ‐β‐ d ‐glucoside, but we observed exclusive formation of the undesired orthoester 5 (Scheme ).…”

“…The 13 C 6 -labeled glucosyl donor [ 13 C 6 ]6 was synthesized starting from [ 13 C 6 ]glucose (14). Acetylation with Ac 2 O and a catalytic amount of FeCl 3 under ultrasonic irradiation gave 15.…”

Mass spectrometry in multi-mycotoxin and fungal spore analysis

“…Leong (2005) synthesized 13 C 11 and 13 C 20 OTA to determine OTA in wine and grapes. Bretz et al (2005) synthesized 3-d 3 -AcDON, in a later study 15-d 1 -DON and developed a method for the analysis of DON and 3-AcDON using HPLC-MS/ MS with these isotopes as internal standards (Bretz et al, 2006). Häubl et al (2006a,b) applied commercially available 13 C 15 DON (Biopure Referenzsubstanzen GmbH, Tulln, Austria) and analysed maize and wheat extracts without any clean up, decreasing their CV values from 115% without an IS to 2.5% with a labelled IS.…”