MASS SPECTROMETRY OF ARALKYL COMPOUNDS WITH A FUNCTIONAL GROUP .6. MASS SPECTRA OF 1-PHENYLETHANOL-1,2-PHENYLETHANOL-1 AND 1-PHENYLPROPANOL-2

Mass spectra of 1‐phenylethanol‐1 and its analogues, specifically deuterated in the aliphatic chain, suggest that the [MCH3]+ ion is represented partly by an α‐hydroxybenzyl fragment. Moreover, the molecular ion loses successively—after scrambling of all hydrogen atoms, except those of CH3a hydrogen atom and C6H6, generation the CH3CO+ ion. Diffuse peaks, found in the spectra of of 2‐phenylethanol‐1 and its analogues, specifically deuterated in the aliphatic chain and in the phenyl ring, show that the molecular ion loses C2H4O, possibly via a four‐center mechanism, after an exchange of aromatic and hydroxylic hydrogens. Mass spectra of 1‐phenylpropanol‐2 and its analogues, specifically, deuterated in the aliphatic chain, demonstrate that in the molecular ion exclusively the hydroxyl hydrogen atom is transferred to one of the ortho‐positions of the phenyl ring via a McLafferty rearrangement, generating the [M  C2H4O]+ ion. Furtherore, an eight‐membered ring structure is proposed for the [M  CH3]+ ion to explain the loss of H2O and C2H2O from this ion after an extensive scrambling of hydrogen atoms. Copyright © 1968 John Wiley & Sons, Ltd.