Accessing pyrrolones and pyridinones: controlling 5-exo and 6-endo ring closures in heterocyclic alkynylamides

2017 ◽  
Vol 95 (4) ◽  
pp. 415-423 ◽  
Author(s):  
Genesis Infante ◽  
Sara Eisler

Competitive 5-exo and 6-endo anionic intramolecular cyclization reactions in heterocyclic alkynylamides were explored via experimental and computational analysis. The 5-exo-dig cyclization pathway is usually disfavoured in heterocyclic systems, and 6-endo products are often both the kinetic and thermodynamic products. However, we’ve found that it is possible to shift selectivity toward the 5-exo-dig pyrrolone products away from the less strained pyridinone products that are produced via the 6-endo-dig cyclization. Parameters such as identity of heteroatom, heteroatom positioning within the heterocycle, and functionality on the alkyne were investigated and, in many cases, were found to strongly influence product ratios. A series of computational studies was performed to provide further insight into the 5-exo-dig and 6-endo-dig pathways in these heterocyclic systems. Theoretical predictions were found to reproduce experimental results, highlighting the predictive capabilities of the computations in determining preferred products.

2019 ◽  
Vol 55 (11) ◽  
Author(s):  
C. S. Akondi ◽  
K. Bantawa ◽  
D. M. Manley ◽  
S. Abt ◽  
P. Achenbach ◽  
...  

Abstract.This work measured $ \mathrm{d}\sigma/\mathrm{d}\Omega$dσ/dΩ for neutral kaon photoproduction reactions from threshold up to a c.m. energy of 1855MeV, focussing specifically on the $ \gamma p\rightarrow K^0\Sigma^+$γp→K0Σ+, $ \gamma n\rightarrow K^0\Lambda$γn→K0Λ, and $ \gamma n\rightarrow K^0 \Sigma^0$γn→K0Σ0 reactions. Our results for $ \gamma n\rightarrow K^0 \Sigma^0$γn→K0Σ0 are the first-ever measurements for that reaction. These data will provide insight into the properties of $ N^{\ast}$N* resonances and, in particular, will lead to an improved knowledge about those states that couple only weakly to the $ \pi N$πN channel. Integrated cross sections were extracted by fitting the differential cross sections for each reaction as a series of Legendre polynomials and our results are compared with prior experimental results and theoretical predictions.


Robotica ◽  
2020 ◽  
pp. 1-24
Author(s):  
Andres Rodriguez Reina ◽  
Kim-Doang Nguyen ◽  
Harry Dankowicz

SUMMARY This paper reports on laboratory and field experimental results for controlled robotic manipulators operating on moving platforms with unmodeled dynamics. The aim is to validate theoretical predictions for the dependence on control parameters of an adaptive control strategy. In addition, the results provide insight into different discretizations of the continuous-time formulation, suggesting the most suitable discretization scheme for hardware implementation. The second set of experimental results, obtained from an implementation of the control framework for synchronization and consensus in networks of robotic manipulators, similarly validate theoretical predictions on the sensitivity to network communication delays.


1969 ◽  
Vol 24 (10) ◽  
pp. 1449-1457
Author(s):  
H. Klingenberg ◽  
F. Sardei ◽  
W. Zimmermann

Abstract In continuation of the work on interaction between shock waves and magnetic fields 1,2 the experiments reported here measured the atomic and electron densities in the interaction region by means of an interferometric and a spectroscopic method. The transient atomic density was also calculated using a one-dimensional theory based on the work of Johnson3 , but modified to give an improved physical model. The experimental results were compared with the theoretical predictions.


2021 ◽  
Vol 11 (1) ◽  
Author(s):  
Michał Ławniczak ◽  
Adam Sawicki ◽  
Małgorzata Białous ◽  
Leszek Sirko

AbstractWe identify and investigate isoscattering strings of concatenating quantum graphs possessing n units and 2n infinite external leads. We give an insight into the principles of designing large graphs and networks for which the isoscattering properties are preserved for $$n \rightarrow \infty $$ n → ∞ . The theoretical predictions are confirmed experimentally using $$n=2$$ n = 2 units, four-leads microwave networks. In an experimental and mathematical approach our work goes beyond prior results by demonstrating that using a trace function one can address the unsettled until now problem of whether scattering properties of open complex graphs and networks with many external leads are uniquely connected to their shapes. The application of the trace function reduces the number of required entries to the $$2n \times 2n $$ 2 n × 2 n scattering matrices $${\hat{S}}$$ S ^ of the systems to 2n diagonal elements, while the old measures of isoscattering require all $$(2n)^2$$ ( 2 n ) 2 entries. The studied problem generalizes a famous question of Mark Kac “Can one hear the shape of a drum?”, originally posed in the case of isospectral dissipationless systems, to the case of infinite strings of open graphs and networks.


1993 ◽  
Vol 16 (2) ◽  
pp. 63-70 ◽  
Author(s):  
N.A. Hoenich ◽  
P.T. Smirthwaite ◽  
C. Woffindin ◽  
P. Lancaster ◽  
T.H. Frost ◽  
...  

Recirculation is an important factor in single needle dialysis and, if high, can compromise treatment efficiency. To provide information regarding recirculation characteristics of access devices used in single needle dialysis, we have developed a new technique to characterise recirculation and have used this to measure the recirculation of a Terumo 15G fistula needle and a VasCath SC2300 single lumen catheter. The experimentally obtained results agreed well with those established clinically (8.5 ± 2.4% and 18.4 ± 3.4%). The experimental results have also demonstrated a dependence on access type, pump speeds and fistula flow rate. A comparison of experimental data with theoretical predictions showed that the latter exceeded those measured with the largest contribution being due to the experimental fistula.


1969 ◽  
Vol 2 (3) ◽  
pp. T29-T33 ◽  
Author(s):  
F. M. Toates

The control systems of accommodation and convergence in the human eye are theoretically examined, together with their interactions which represent accommodative convergence and convergence induced accommodation. A control model is proposed in order to help to understand the system, and it is used to make predictions concerning accommodation and convergence placed in conflict, monocular vision, fusional after-effects and the effect of age and drugs on accommodation and accommodative convergence. In each case the theoretical predictions are compared with established experimental results.


ChemInform ◽  
2010 ◽  
Vol 22 (3) ◽  
pp. no-no
Author(s):  
O. I. KOLODYAZHNYI ◽  
E. V. GRISHKUN ◽  
V. I. YAKOVLEV ◽  
V. P. KUKHAR'

Sign in / Sign up

Export Citation Format

Share Document