title: 4-(9-fluorenylmethyloxycarbonyl)phenylhydrazine (FmPH): a new chromophoric reagent for quantitative monitoring of solid-phase aldehydes(1-3).
abstract: 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 (epsilon(301nm) = 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).
authors.affiliation: Department of Chemistry, University of Minnesota, 207 Pleasant Street S E, Minneapolis, Minnesota 55455, USA.
authors.forename: Simon K
authors.initials: SK
authors.lastname: Shannon
authors.forename: George
authors.initials: G
authors.lastname: Barany
mesh_terms: D000447:Aldehydes / Q000737:chemistry*; D000586:Amination; D002384:Catalysis; D002625:Chemistry, Organic / Q000379:methods*; D003432:Cross-Linking Reagents / Q000032:analysis / Q000138:chemical synthesis*; D007202:Indicators and Reagents; D007700:Kinetics; D015394:Molecular Structure; D010084:Oxidation-Reduction; D010659:Phenylhydrazines / Q000032:analysis / Q000138:chemical synthesis*
chemical_list: C488418:4-(9-fluorenylmethyloxycarbonyl)phenylhydrazine; D000447:Aldehydes; D003432:Cross-Linking Reagents; D007202:Indicators and Reagents; D010659:Phenylhydrazines