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RDA Fragmentation Research

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Still another example showing a RDA fragmentation phenomenon is the mass spectrum of 5,7dihydroxy -4- methoxyisoflavanone.
(C16 H14 O5 M 286)
In this molecular ion cleavage occur through RDA reaction. In the ionization process ene and diene with charges are formed. The base peak is at m/z 134, is due to the ene and the diene is at m/z 152, these fractions favor the fallowing mechanism, with the dissociation of ring present in the compound.

From the study of mass spectrum of Isoflavanone, masses and structures of the fragments ene, and diene can be ascertained, and from this the structure of compound can be determined. The position of substituent on the ring, can be determined by preparing the derivatives and studying the mass spectrum of these derivatives with a known substituent in the fragment ene …show more content…

These substances show a RDA cleavage-phenomenon in their mass spectrum, and through this their structure and molecular formula are determined.

THE MacLofferty REARRANGMENT FRAGMENTATION PROCESS
Basically the hetero atom, or functional group in a molecule facilitate the fragmentation, and it is expressed with α-cleavage. In MacLofferty rearrangement the essential feature is the double bond, with or without heteroatom, with a γ-hydrogen. This type of arrangement is commonly encountered in the compounds, with C-(carboxylic acid, esters, aldehydes ketones, amides, lactams, lactones) compounds with C=N (azomethines, or shiffs base, hydrazones, oximes, semicarbazones) compounds with S=O, (sulfonic acid esters) and compounds with C=C (alkylarene, alkylhetero cycles, benzyl ethers, olefene).
In MacLafferty cleavage, H-atom at γ-position to double bond, transfer to double bond via six-member ring formation, and simultaneously double bond moves in between the adjacent atoms, and a part of molecule fragment detach from the molecule, the mechanism of fragmentation is as

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