Mass spectrometry of sterols. Electron ionization induced fragmentation of C-4-alkylated cholesterols.
The electron impact ionization of C-4-alkylated cholest-5-en-3beta-hydroxysterols has been investigated. The mass spectra of the C-4-alkylated cholesterols contain a number of ions in the high mass region for which analogous ions are not found in the spectrum of cholesterol. Detailed studies of the composition and origin of these ions have been made by high resolution mass spectrometry and analysis of metastable ions. In addition, a large number of isotopically (deuterium and 18O) substituted C-4-alkylated analogues have been prepared to assist in the interpretation of the spectra. The combined results indicate the occurrence of a number of very complex and unusual electron ionization induced fragmentations. Most notable of the findings reported herein concerns the demonstration of the formation of an ion involving loss of the elements of ring A with an intramolecular shift of the oxygen and hydrogen atoms of the hydroxyl function to the charge-retaining species.
ELECTRON-IMPACT INDUCED REARRANGEMENT REACTIONS OF ORGANIC MOLECULES.
Hydrogen migrations accompany many mass spectrometric fragmentation processes and a detailed study of these migrations, largely by means of deuterium labeling, has shed much light on electron-impact induced bond fissions. More recently, it has been found that groups other than hydrogen, such as alkyl, aryl, hydroxyl, etc., also can migrate after electron bombardment and the present article is concerned with a discussion of such molecular rearrangements among organic compounds. These observations are not only of intrinsic mechanistic interest, but a detailed knowledge of the occurrence of such migration reaction is crucial to the proper interpretation of mass spectra and to the avoidance of misinterpretations in “element mapping”.
Fragment Rotational State Distributions From The Dissociation Of NeIBr: Experimental And Theoretical Results
The IBr fragment rotational state distributions that result when the NeIBr van der Waals molecule undergoes vibrational predissociation have been measured in a pump–probe laser‐induced fluorescence experiment. Independent of initial vibrational state and the number of quanta of vibrational energy lost from the I–Br coordinate, the rotational distributions extend over the full range of energetically accessible states. From the observation of energetic constraints on the rotational distribution, the dissociation energy (D0) is calculated to be 65.5±1.2 cm−1 for the A electronic state, v=16. For the X electronic state, v=0, D0=71.8±1.2 cm−1. Quantum mechanical bound state calculations carried out on a model A electronic state potential energy surface are in quantitative agreement with this result. The rotational distributions are broader than that predicted by either a Franck–Condon or classical impulsive model for the dissociation. The distributions are qualitatively in accord with classical trajectory calc...