Search results for "OXETANE"

A surface hopping algorithm for nonadiabatic minimum energy path calculations

2015

The article introduces a robust algorithm for the computation of minimum energy paths transiting along regions of near-to or degeneracy of adiabatic states. The method facilitates studies of excited state reactivity involving weakly avoided crossings and conical intersections. Based on the analysis of the change in the multiconfigurational wave function the algorithm takes the decision whether the optimization should continue following the same electronic state or switch to a different state. This algorithm helps to overcome convergence difficulties near degeneracies. The implementation in the MOLCAS quantum chemistry package is discussed. To demonstrate the utility of the proposed procedur…

DFT study on the cycloreversion of thietane radical cations.

2011

The molecular mechanism of the cycloreversion (CR) of thietane radical cations has been analyzed in detail at the UB3LYP/6-31G* level of theory. Results have shown that the process takes place via a stepwise mechanism leading to alkenes and thiobenzophenone; alternatively, formal [4 + 2] cycloadducts are obtained. Thus, the CR of radical cations 1a, b(center dot+) is initiated by C2-C3 bond breaking, giving common intermediates INa,b. At this stage, two reaction pathways are feasible involving ion molecule complexes IMCa,b (i) or radical cations 4a,b(center dot+) (ii). Calculations support that 1a(center dot+) follows reaction pathway (leading to the formal [4 + 2] cycloadducts 5a). By cont…

Synthesis of Oxetane-Functional Aliphatic Polyesters via Enzymatic Polycondensation

2012

Synthesis, characterization, and thermal properties of a series of oxetane-functional aliphatic polyesters are investigated. The incorporation of the acid-sensitive 3,3-bis(hydroxymethyl)oxetane (BHMO) into polymers is achieved by using the enzyme CALB (Candida antarctica Lipase B) as a catalyst. This mild synthetic strategy provides well-defined, oxetane-functional polyesters. The enzymatic polycondensation allows for the synthesis of a series of aliphatic polyesters containing various ratios of the difunctional monomers sebacic acid, 1,8-octanediol, and BHMO with molecular weights between 5000–9800 g mol−1 and polydispersity indices (Mw/Mn) in the range of 1.25 and 1.92. Furthermore, cros…

Two novel oxetane containing lignans and a new megastigmane from Paronychia arabica and in silico analysis of them as prospective SARS-CoV-2 inhibito…

2021

The chemical characterization of the extract of the aerial parts of Paronychia arabica afforded two oxetane containing lignans, paronychiarabicine A (1) and B (2), and one new megastigmane, paronychiarabicastigmane A (3), alongside a known lignan (4), eight known phenolic compounds (5–12), one known elemene sesquiterpene (13) and one steroid glycoside (14). The chemical structures of the isolated compounds were constructed based upon the HRMS, 1D, and 2D-NMR results. The absolute configurations were established via NOESY experiments as well as experimental and TDDFT-calculated electronic circular dichroism (ECD). Utilizing molecular docking, the binding scores and modes of compounds 1–3 tow…

Aliphatic Polyethers: Classical Polymers for the 21st Century.

2015

Polyethers-polymers with the structural element (R'-O-R)n in their backbone--are an old class of polymers which were already used at the time of the ancient Egyptians. However, still today these materials are highly important with applications in all areas of our life, reaching from the automotive and paper industry to cosmetics and biomedical applications. In this Review, different aliphatic polyethers like poly(epoxide)s, poly(oxetane)s, and poly(tetrahydrofuran) are discussed. Special emphasis is placed on the history, the polymerization techniques (industrially and in academia), the properties, the applications as well as recent developments of these materials.

Frontispiece: Recent Advances in Enantioselective Desymmetrizations of Prochiral Oxetanes

2021

Chemische charakterisierung des kettenaufbaus und kristallisationsverhaltens von copolymeren aus 3,3-bis(chlormethyl)oxetan und β-propiolacton

1974

Aus 3,3-Bis(chlormethyl)oxetan (1) und β-Propiolacton (2) wurden durch kationische Polymerisation Copolymere hergestellt, in denen Propiolactoneinheiten bis zu einem Molenbruch von 0,16 eingebaut sind. Das Copolymerisationsverhalten wurde untersucht, und die Copolymerisationsparameter wurden bestimmt. Die Copolymeren wurden kristallisiert und die Einkristalle hinsichtlich ihrer Zusammensetzung und Morphologie charakterisiert. Durch selektive Umesterung in den amorphen Bereichen der suspendierten Einkristalle wurde die Verteilung der aus β-Propiolacton gebildeten Einheiten (PL) uber den Kristall untersucht, und die Ergebnisse mit Abbauversuchen an den gelosten Copolymeren wurden verglichen. …