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Localization of double and triple bonds in linear conjugated enyne‐acetates and alcohols
Author(s) -
Einhorn J.,
Virelizier H.,
Guerrero A.,
Tabet J. C.
Publication year - 1985
Publication title -
biomedical mass spectrometry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.475
H-Index - 121
eISSN - 1096-9888
pISSN - 0306-042X
DOI - 10.1002/bms.1200120504
Subject(s) - enyne , conjugated system , chemistry , double bond , medicinal chemistry , triple bond , stereochemistry , ring (chemistry) , tetrahydropyran , catalysis , organic chemistry , polymer
Localization of double and triple bonds in linear conjugated enyne‐acetates and alcohols can be achieved in microgram scale through a two‐step reaction sequence: epoxidation followed by catalytic hydrogenation or deuteration. This derivatization yields a saturated secondary alcohol of RCHOH(CH 2 ) n OR'type (R = CH 3 (CH 2 ) m , R' = H, COCH 3 ), by regiospecific ring opening reaction of the intermediate epoxide. The position of the hydroxyl group is clearly defined by the [MR] + and subsequent ions observed in the electron impact (EI) mass spectrum. The unequivocal location of the conjugated enyne system can be effected by comparing the pattern and position of the [MR] + ion(s) found under hydrogenation and deuteration conditions, since the same secondary alcohol may proceed from two isomeric enyne structures, i.e. CH 3 (CH 2 ) m CHCHCC(CH 2 ) n−3 OR' (enyne A) and CH 3 (CH 2 ) m‐3 CCCHCH(CH 2 ) n OR' (enyne B). Metastable (mass‐analysed ion kinetic energy (MIKE), HV scan) mass spectra and gas phase labelling were used for filiation attribution and mechanisms.