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Elimination of water from the molecular ion of cycloheptanol
Author(s) -
Tureček František,
Smutek Miloš,
Hanuš Vladimír
Publication year - 1981
Publication title -
organic mass spectrometry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.475
H-Index - 121
eISSN - 1096-9888
pISSN - 0030-493X
DOI - 10.1002/oms.1210161103
Subject(s) - chemistry , fragmentation (computing) , hydrogen atom , ring (chemistry) , cleavage (geology) , deuterium , hydrogen , stereospecificity , ion , elimination reaction , hydroxyl radical , stereochemistry , medicinal chemistry , group (periodic table) , radical , organic chemistry , catalysis , materials science , atomic physics , fracture (geology) , computer science , operating system , physics , composite material
Under electron impact cycloheptanol decomposes by four fragmentation paths: (1) α‐cleavage with subsequent losses of C 1 ‐C 5 fragments, (2) elimination of water, (3) loss of the hydrogen atom from C‐1 and (4) loss of the hydroxyl group. The mechanism of water elimination was investigated by means of deuterium labelling. 1,4‐Elimination of water predominates in cycloheptanol, with the stereospecific cis ‐1,3‐elimination also being operative. The loss of water is preceded by extensive exchange of the hydroxyl hydrogen with those of the ring. This is attributed to a very facile transannular interaction of the hydroxyl group with the C‐3 to C‐6 positions that are made accessible due to conformational properties of the 7‐membered ring. A kinetic model is proposed, describing migrations of the ring hydrogen atoms.