C. Shimasaki et al., PYROLYSIS AND MASS-SPECTRA OF TRIMETHYLSILYL DERIVATIVES OF MONOSACCHARIDES, Journal of thermal analysis, 44(4), 1995, pp. 855-867
The pyrolysis of trimethylsilyl derivatives of saccharides (1) was inv
estigated by DTA-TG, MS, GC/MS and TG-GC/MS. The DTA-TG/DTG curves sho
wed that the pyrolysis of 1 occurred in one stage. The exothermic peak
s were due to sublimation or thermal decomposition by vaporization. Th
e cleavage mechanism by electron impact of 1 was classified into four
categories: 1) stepwise elimination of the side-chain, 2) cleavage sf
the side-chain, 3) cleavage of the pyranose ring, and 4) cleavage of t
he pyranose ring and side-chain at the same time. The mass-spectrum fo
r 1 revealed the main common four fragment ions, such as m/z 73, 191,
204 and 217, with cleavage of the pyranose ring. These fragment ions w
ere detected with a similar retention time in the gas cromatogram by G
C/MS or TG-GC/MS. The retention time for 1 increased in the sequence a
ldopentose < ketohexose < aldohexose. This result indicates that the t
rimethylsilyl derivatives are thermally stable. Subsequently, the pyro
lysis regime for 1 obeyed apparent 1/2-order kinetics and their appare
nt activation energy was estimated as 75-100 kJ/mole.