TY - JOUR
T1 - 4-(9-Fluorenylmethyloxycarbonyl)phenylhydrazine (FmPH)
T2 - A new chromophoric reagent for quantitative monitoring of solid-phase aldehydes
AU - Shannon, Simon K.
AU - Barany, George
PY - 2004/7/9
Y1 - 2004/7/9
N2 - A direct method for quantifying solid-phase aldehydes has been developed, using a new reagent, 4-(9-fluorenylmethyloxycarbonyl)phenylhydrazine (FmPH). The FmPH reagent was synthesized in three steps (24% overall yield) from commercially available p-hydrazinobenzoic acid. Resin-bound aldehydes reacted quantitatively with FmPH, in the presence of trimethylorthoformate (TMOF) as a dehydrating agent, to form a highly conjugated, immobilized FmPH-hydrazone. Next, mild treatment of the hydrazone with an excess of piperidine-N,N- dimethylformamide (1:1) released the piperidine-dibenzofulvene adduct chromophore (ε301nm = 7800 M-1 cm-1) from the support. FmPH quantitation of aldehydes proved to be a straightforward, sensitive, and reproducible technique for monitoring resin-bound aldehydes [albeit insufficiently reactive to allow reliable quantification of ketones]. The FmPH aldehyde assay is applicable to a range of solid supports, as demonstrated specifically for poly(ethylene glycol)-polystyrene (PEG-PS), aminomethylpolystyrene (AMP), and cross-linked ethoxylate acrylate resin (CLEAR).
AB - A direct method for quantifying solid-phase aldehydes has been developed, using a new reagent, 4-(9-fluorenylmethyloxycarbonyl)phenylhydrazine (FmPH). The FmPH reagent was synthesized in three steps (24% overall yield) from commercially available p-hydrazinobenzoic acid. Resin-bound aldehydes reacted quantitatively with FmPH, in the presence of trimethylorthoformate (TMOF) as a dehydrating agent, to form a highly conjugated, immobilized FmPH-hydrazone. Next, mild treatment of the hydrazone with an excess of piperidine-N,N- dimethylformamide (1:1) released the piperidine-dibenzofulvene adduct chromophore (ε301nm = 7800 M-1 cm-1) from the support. FmPH quantitation of aldehydes proved to be a straightforward, sensitive, and reproducible technique for monitoring resin-bound aldehydes [albeit insufficiently reactive to allow reliable quantification of ketones]. The FmPH aldehyde assay is applicable to a range of solid supports, as demonstrated specifically for poly(ethylene glycol)-polystyrene (PEG-PS), aminomethylpolystyrene (AMP), and cross-linked ethoxylate acrylate resin (CLEAR).
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U2 - 10.1021/jo049830b
DO - 10.1021/jo049830b
M3 - Article
C2 - 15230579
AN - SCOPUS:3042819410
SN - 0022-3263
VL - 69
SP - 4586
EP - 4594
JO - Journal of Organic Chemistry
JF - Journal of Organic Chemistry
IS - 14
ER -