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Mass Spectrometric Identification of New Derivatives of PGA's and 19‐hydroxy‐PGA's Specific for Multiple Ion Detection
Author(s) -
Roselló J.,
Sunol C.,
Gelpi E.
Publication year - 1978
Publication title -
israel journal of chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.908
H-Index - 54
eISSN - 1869-5868
pISSN - 0021-2148
DOI - 10.1002/ijch.197800029
Subject(s) - chemistry , bstfa , piperidine , morpholine , amine gas treating , pyrrolidine , methylamine , nucleophile , medicinal chemistry , mass spectrometry , stereochemistry , organic chemistry , chromatography , derivatization , catalysis
The mass spectra of the new piperidyl‐PGA (TMS), derivatives, formed by reaction of prostaglandin A 1 or A 2 with BSTFA/piperidine, are characterized by a dominant M − 173 ion, remarkably specific for MID applications. Similar derivatives have also been obtained with mixtures of BSTFA and other heterocyclic amines (hexamethylenimine, pyrrolidine, morpholine and propylenimine), which give the respective heterocycle‐PGA (TMS), derivatives. Likewise, the corresponding 11‐piperidyl‐19‐OH‐PGA (TMS) 4 seem specially suited for the selected ion detection of PGA “artifacts” in extracts of human semen. The postulated structure of fragments at M − 173 and M − 423 (series I) and M − 425 (series II) is in favour of a pushpull type of reaction mechanism leading to these derivatives by nucleophilic addition of the amine on the C‐11 atom of the PGA's and concurrent formation of an enolate ion from the 9‐keto group with silanization of all reactive groups by BSTFA. An example of an application to the determination of PGA's and 19‐OH‐PGA's in a biological extract is given.