Regioselective homolytic substitution of benzo[c][2,7]naphthyridines

Benzo[c][2,7]naphthyridines bearing electron-withdrawing substituents (bromo, acetyl) at C-4 undergo regioselective homolytic substitutions at C-5 with nucleophilic 1,3,5-trioxanyl and ethoxycarbonyl radicals under Minisci conditions. Surprisingly, mainly 5,6-dihydro derivatives are formed in these reactions. Rearomatization with manganese dioxide leads to 4,5-disubstituted benzo[c][2,7]naphthyridines, which should be attractive building blocks for the synthesis of pyridoacridine alkaloids. Homolytic methylation at C-5 takes place with methyl radicals generated from acetic acid and acetaldehyde, respectively.     

Car sequencing versus mixed-model sequencing: A computational study

The paper deals with the two most important mathematical models for sequencing products on a mixed-model assembly line in order to minimize work overload the mixed-model sequencing (MMS) model and the car sequencing (CS) model. Although both models follow the same underlying objective, only MMS directly addresses the work overload in its objective function. CS instead applies a surrogate objective using so-called sequencing rules which restrict labor-intensive options accompanied with the products in the sequence. The CS model minimizes the number of violations of the respective sequencing rules, which is widely assumed to lead to minimum work overload. This paper experimentally compares CS with MMS in order to quantify the gap in the solution quality between both models. The paper studies several variants of CS with different sequencing rule generation approaches and different objective functions from the literature as well as a newly introduced weighting factor. The performance of the different models is evaluated on a variety of random test instances. Although the objectives of CS and MMS are positively linearly correlated, results show that a sequence found by CS leads to at least 15% more work overload than a solution found by MMS. For none of the considered test instances and for none of the three different objective functions, CS is able to produce competitive results in terms of solution quality (work overload) compared to MMS. The results suggest that decision makers using CS should investigate whether MMS would lead to better sequencing orders for their specific instances.     

A Dynamic Analysis of Schelling’s Binary Corruption Model: A Competitive Equilibrium Approach

Schelling (in Micromotives and Macrobehavior, Norton, New York, 1978) suggested a simple binary choice model to explain the variation of corruption levels across societies. His basic idea was that the expected profitability of engaging in corruption depends on its prevalence. The key result of the so-called Schelling diagram is the existence of multiple equilibria and a tipping point. The present paper puts Schelling’s essentially static approach into an intertemporal setting. We show how the existence of an unstable interior steady state leads to thresholds such that history alone or history in addition to expectations (or coordination) is necessary to determine the long-run outcome. In contrast to the related literature, which classifies these two cases according to whether the unstable equilibrium is a node or a focus, the actual differentiation is more subtle because even a node can lead to an overlap of solution paths such that the initial conditions alone are insufficient to uniquely determine the competitive equilibrium. Another insight is that a (transiently) cycling competitive equilibrium can dominate the direct and monotonic route to a steady state, even if the direct route is feasible.     

A New Furan Synthesis. Evidence for the Intermediacy of the Elusive Anhydro-5-hydroxy-1,3-dioxolium Hydroxide System

While five-membered mesoionic ring systems have been employed as useful synthetic intermediates in the preparation of a wide variety of pyrroles and thiophenes¹, only limited application has been made to the preparation of furans². We would like to report a new furan synthesis in which the unreported anhydro-5-hydroxy-1, 3-dioxolium hydroxide system may be an intermediate.     

Regioselective Bromination of a Thymine–Acridine Conjugate by N-Bromosuccinimide

A thymine and acridine conjugate (1), containing a benzylic carbon of thymine and an electron-rich aromatic ring (acridine) within the same molecule, was synthesized. Treatment of 1 with N-bromosuccinimide (NBS) in anhydrous chloroform in the presence of azobisisobutylnitrile produced a dibromo-substituted thymine–acridine conjugate (7) as a major product, in which the bromination was only observed on the acridine ring. Nuclear Overhauser effect (NOE) difference spectroscopy revealed that the actual bromination substitution was on C-2 and C-7 of acridine. Our results suggest that electrophilic aromatic substitution, not the expected benzylic radical reaction, takes place predominantly even when 1 is subjected to the NBS reaction condition, which favors radical processes. In addition, such selectivity is clearly solvent dependent.