Electrospray ionization (ESI) fragmentations and dimethyldioxirane reactivities of three diverse lactams having full, half, and zero resonance energies.

Clicks: 305
ID: 238228
2014
Article Quality & Performance Metrics
Overall Quality
Not rated
Combines reader engagement with the AI quality analysis. This article has not been analysed, so there is no overall score — reader engagement is measured and shown alongside.
AI Quality Assessment
Not analyzed
Readership in this journal
Steady

Ranked #29 of 103 articles by views in The Journal of organic chemistry

Most read Least read

Bar heights use a square-root scale.

Mint this article as an NFT
Not yet minted

Create a permanent, verifiable on-chain record of this article on the Scimatic Network. The NFT is held in your Journament account, and you can withdraw it to your own wallet at any time.

5 SUSD one-off · no wallet required
Sign in to mint
Abstract
Three lactams having, respectively, ~20, ~10, and 0 kcal/mol of resonance energy have been subjected to electrospray ionization mass spectrometry (ESI/MS) as well as to attempted reaction with dimethyldioxirane (DMDO). The ESI/MS for all three lactams are consistent with fragmentation from the N-protonated, rather than the O-protonated tautomer. Each exhibits a unique fragmentation pathway. DFT calculations are employed to provide insights concerning these pathways. N-Ethyl-2-pyrrolidinone and 1-azabicyclo[3.3.1]nonan-2-one, the full- and half-resonance lactams, are unreactive with DMDO. The "Kirby lactam" (3,5,7-trimethyl-1-azaadamantan-2-one) has zero resonance energy and reacts rapidly with DMDO to generate a mixture of reaction products. The structure assigned to one of these is the 2,2-dihydroxy-N-oxide, thought to be stabilized by intramolecular hydrogen bonding and buttressing by the methyl substituents. A reasonable pathway to this derivative might involve formation of an extremely labile N-oxide, in a purely formal sense, an example of the hitherto-unknown amide N-oxides, followed by hydration with traces of moisture.
Reference Key
morgan2014electrospraythe Use this key to autocite in the manuscript while using SciMatic Manuscript Manager or Thesis Manager
Authors Morgan, Kathleen M;Ashline, David J;Morgan, Jessica P;Greenberg, Arthur;
Journal The Journal of organic chemistry
Year 2014
DOI
10.1021/jo402041u
URL
Keywords
photochemistry reactivity polyolefins diels–alder reactions bromination epoxidation hydrogenation

Citations

No citations found. To add a citation, contact the admin at info@scimatic.org

Comments

No comments yet. Be the first to comment on this article.