Liu, Jin published the artcileA Comparison of Acetyl- and Methoxycarbonylnitrenes by Computational Methods and a Laser Flash Photolysis Study of Benzoylnitrene, Application of 2-Methoxyacetamide, the main research area is acetylnitrene methoxycarbonylnitrene comparison laser flash photolysis benzoylnitrene.
D. functional theory (DFT), CCSD(T), and CBS-QB3 calculations were performed to understand the chem. and reactivity differences between acetylnitrene (CH3C(:O)N) and methoxycarbonylnitrene (CH3OC(:O)N) and related compounds CBS-QB3 theory alone correctly predicts that acetylnitrene has a singlet ground state. We agree with previous studies that there is a substantial N-O interaction in singlet acetylnitrene and find a corresponding but weaker interaction in methoxycarbonylnitrene. Methoxycarbonylnitrene has a triplet ground state because the oxygen atom stabilizes the triplet state of the carbonyl nitrene more than the corresponding singlet state. The oxygen atom also stabilizes the transition state of the Curtius rearrangement and accelerates the isomerization of methoxycarbonylnitrene relative to acetylnitrene. Acetyl azide is calculated to decompose by concerted migration of the Me group along with nitrogen extrusion; the free energy of activation for this concerted process is only 27 kcal/mol, and a free nitrene is not produced upon pyrolysis of acetyl azide. Methoxycarbonyl azide, on the other hand, does have a preference for stepwise Curtius rearrangement via the free nitrene. The bimol. reactions of acetylnitrene and methoxycarbonylnitrene with propane, ethylene, and methanol were calculated and found to have enthalpic barriers that are near zero and free energy barriers that are controlled by entropy. These predictions were tested by laser flash photolysis studies of benzoyl azide. The absolute bimol. reaction rate constants of benzoylnitrene were measured with the following substrates: acetonitrile (k = 3.4 × 105 M-1 s-1), methanol (6.5 × 106 M-1 s-1), water (4.0 × 106 M-1 s-1), cyclohexane (1.8 × 105 M-1 s-1), and several representative alkenes. The activation energy for the reaction of benzoylnitrene with 1-hexene is -0.06 ± 0.001 kcal/mol. The activation energy for the decay of benzoylnitrene in pentane is -3.20 ± 0.02 kcal/mol. The latter results indicate that the rates of reactions of benzoylnitrene are controlled by entropic factors in a manner reminiscent of singlet carbene processes.
Journal of Organic Chemistry published new progress about Electron spin density. 16332-06-2 belongs to class ethers-buliding-blocks, name is 2-Methoxyacetamide, and the molecular formula is C3H7NO2, Application of 2-Methoxyacetamide.
Referemce:
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Ether | (C2H5)2O – PubChem