Does the electron ionization induced fragmentation of partly saturated stereoisomeric pyrrolo- and isoindoloquinazolinones show stereospecificity?
The electron ionization mass spectrometric behavior of pyrroloquinazolinones (1-6) and isoindoloquinazolinones (7-14) was studied. These compounds were further classified as partly saturated pyrroloquinazolinones (1-3), benzologues (7-11), methylene-bridged derivatives (4-6, 12, 13) and a bisacyl compound (14). The mass spectra of the pyrrolo- and isoindoloquinazolinones did not exhibit stereospecific retro-Diels-Alder (RDA) fragmentations. The cyclohexane-fused compounds 7 (cis annelated) and 8 (trans annelated) did display some other ions differing in their abundances that could be used to differentiate this pair of stereoisomers. Also the cyclohexene-fused compounds 2, 3, 9 and 10 exhibited somewhat different ion abundances pairwise that could be utilized for isomeric differentiation. Earlier hypothesis of pyrrolo ring cleavage via the loss of C(3)H(5)O(.) was strengthened by the fragmentation of compounds 1-4. RDA(+/-H) fragmentation is more favorable than the formation of [M-R](+) ions (R=H, C(6)H(4)CH(3), or C(6)H(4)Cl) when an unsaturated bicyclic group is present but both RDA fragmentation and [M-R](+) formation occur for cyclohexene-fused compounds, possibly because of the lower ring strain than with norbornene-fused compounds. The [M-H](+) ion was abundant for compounds 7 and 8 as was [M-Ar](+) for 1-4 and 11. Although the compounds studied might participate in amide-imidol tautomerism, no indication of such tautomerism was detected.
Pihlaja
Kalevi
K
Structural Chemistry Group, Department of Chemistry, University of Turku, FI-20014 Turku, Finland.
Martiskainen
Olli
O
Stájer
Géza
G
D002626:Chemistry, Pharmaceutical; D004364:Pharmaceutical Preparations; D011799:Quinazolines / Q000737:chemistry*; D021241:Spectrometry, Mass, Electrospray Ionization; D013237:Stereoisomerism
D004364:Pharmaceutical Preparations; D011799:Quinazolines