Is the collision induced loss of ethene from the (M – H+)− ion of butyrophenone a γ-hydrogen rearrangement?

1986 ◽  
Vol 64 (4) ◽  
pp. 764-768 ◽  
Author(s):  
Michael B. Stringer ◽  
Dennis J. Underwood ◽  
John H. Bowie ◽  
John L. Holmes ◽  
Alexander A. Mommers ◽  
...  

The (M – H+)− ion of butyrophenone undergoes the following reactions on collisional activation: losses of CH3•, CH4, (C,H5•), C2H4, C3H7•, (CO + CH4), together with formation of C6H5− and C4H5O−. Labelling studies (13C and 2H) show that the losses of CH3•, C3H7• and the formation of C6H5− and C4H5O− are specific and occur without hydrogen scrambling. All other reactions involve prior or accompanying hydrogen rearrangement. In particular, the loss of C2H4 is very complex: it involves loss of ethyl carbon atoms, but all hydrogen atoms are involved via specific rearrangement reactions. The phenyl–alkyl H rearrangements which are noted for this process occur after collisional activation of the (M – H+)− ion.

1975 ◽  
Vol 53 (21) ◽  
pp. 3175-3187 ◽  
Author(s):  
Don C. DeJongh ◽  
Denis C. K. Lin ◽  
Pierre LeClair-Lanteigne ◽  
Denis Gravel

An interesting rearrangement has been observed in the mass spectra of a series of N-benzoyl-2-hydroxyalkylamines. The hydrogen atom of the hydroxyl group is transferred to the N-benzoyl portion of the molecular ion and the bond between positions 1 and 2 in the N-alkyl group is cleaved. A rearrangement ion, observed at m/e 135, is formed along with a neutral aldehyde or ketone. When the hydroxylic hydrogen is replaced by a trimethylsilyl substituent, the latter group is transferred with comparable efficiency. Differences in the relative importance of this rearrangement in the mass spectra of a series of related compounds with decreasing substitution at position 2, have been explained by differences in the stabilities of the neutral molecules formed along with m/e 135 and by the occurrence of a double hydrogen rearrangement which competes if hydrogen atoms are present in a relationship gamma and delta to the carbonyl group.


1990 ◽  
Vol 43 (12) ◽  
pp. 2027 ◽  
Author(s):  
MJ Alexander ◽  
JH Bowie ◽  
RN Hayes

Rearrangement reactions involving hydride and methyl anion migrations are observed when certain enolate ions derived from isopropyl and t- butyl ketones are subjected to collisional activation. For example (i) -CH2CO-i-C3H7 → -(CH2CHO)+C3H6 and (ii) -CH2CO-t-C4H9 → -(CH2COCH3)+C3H6The mechanisms of these and related reactions have been investigated by denterium labelling and product ion studies.


2006 ◽  
Vol 110 (51) ◽  
pp. 14013-14017 ◽  
Author(s):  
Clotilde S. Cucinotta ◽  
Alice Ruini ◽  
Alessandra Catellani ◽  
András Stirling

1972 ◽  
Vol 25 (5) ◽  
pp. 1107 ◽  
Author(s):  
JH Bowie ◽  
GE Gream ◽  
M Mular

Carbon and hydrogen scrambling occurs either prior to, or during, the decompositions of the ions C9H9+, CllH13+, and C12H15+ in the first field-free region of the mass spectrometer. The ions may be produced from various substrates, and the decompositions of CllH13+ may be interpreted in terms of a decomposing ion in which some, but not all, of the C-H bonds have broken and reformed. The ions C9H9+ and C10H11+ may be produced by complex hydrogen rearrangement in the side-chain of particular bromo-and hydroxy-alkylcyclooctatetraene derivatives.


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