Etude par Spectrométrie de Masse de la Fragmentation d'une Série de Diols Aliphatiques

Abstract

The mass spectrometric fragmentation of a series of diols having the general formula HO-(CH2).-OH with n=2-11 has been studied. Extensive labelling of n-bntane-1,4 diol and n-hexane-1,6 diol with deuterium allows fragmentation modes to be proposed. The labelling reveals that intramolecular exchange of H atoms often precedes the fragmentation and becomes more important when the length of the chain increases.La fragmentation d'une sCrie de diols aliphatiques de formule gCnCrale HO-(CHJn-OH avec n=2-11 a CtC CtudiCe B l'aide de molCcules marqukes avec du deutCrium. Les marquages du n-butanediol-1,4 et du n-hexanediol-1,6 ont notamment permis de mettre en Cvidence des rCactions d'Cchange intramolCculaire d'hydrogkne; ces Cchanges deviennent plus importants avec l'allongement de la chaine.

Effects of functional group interactions on the bimolecular and dissociation reactions of diols

“…istorically, the influence of neighboring-group interactions has been an active area of research in organic chemistry in solution [1]. Likewise, there have been numerous accounts of the importance of functional group interactions of many types of difunctional molecules [2][3][4][5][6][7][8][9][10][11][12][13][14][15][16][17][18], including diols [2][3][4][5][6][7][8][9][10][11][12], diacids [13], diesters [14], and amino alcohols [15], in gas-phase reactions with positive ions. Perhaps the most relevant to the present work are those involving the interactions between hydroxyl groups.…”

“…There have been numerous mass-spectrometric investigations of diols, mostly cyclic ones [2][3][4][5][6][7][8][9][10][11][12]. Some of these studies have concerned the influence of hydroxyl group interactions on the mass spectra generated by electron ionization (EI) or chemical ionization (CI) of various diols.…”