Mechanisms of sulfanyl (RS) migrations: synthesis of heterocycles

Thiiranium (episulfonium) ions had been acknowledged as reaction intermediates for many years, but it was not until 1977 that Nicolaou demonstrated systematically that these reactive heterocyclic cations could be trapped by carboxylic acids to give lactones. In the years that followed this report, extensive research greatly extended the scope of this reaction, particularly with regard to the methods for generating thiiranium ions, the types of nucleophiles that are compatible with this reaction, and the selectivity involved in the cyclization reactions. For many years we have been using thiiranium ions for the synthesis of saturated heterocycles. Whereas Nicolaou's method relied on electrophilic sulfenylation of alkenes, we have generated thiiranium ions by displacement of a leaving group with neighboring-group participation by a sulfanyl group. Many of the examples we have reported are of cyclizations that are reversible and so where two (and in some cases more) products can result, the outcome of the reactions provides fundamental information about the relative stability of different heterocyclic ring systems. This Review will begin with a brief introduction to sulfanyl participation as a method for generating thiiranium (and thiolanium) ions, and will go on to explore the idea of using sulfanyl migrations in synthesis. Initially, emphasis will be placed on mechanisms of [1,2] sulfanyl migrations: we will look specifically at [1,2] sulfanyl migrations (usually PhS) with elimination, substitution, and cyclization. Emphasis will then shift to the factors that affect the outcome of cyclization reactions. In particular, we will cover cyclizations with hydroxy nucleophiles and examine situations in which there are more than one hydroxy nucleophile present. We will also examine cyclizations with other nucleophiles, namely amines and sulfides. After our discussion of [1,2] sulfanyl migrations, we will look very briefly at the scope of [1,4] sulfanyl participation, before finally drawing up some guidelines that (we hope) will help other organic chemists take advantage of the rearrangement reactions that the sulfanyl group has to offer.     

The effect of liquid crystal structure on the rheological properties of nitrocellulose-dimethylacetamide solutions

Solutions of Pyro grade nitrocellulose (NC) in dimethyl acetamide (DMA), containing between 42.5% and 60% NC (w/w), have been studied by differential scanning calorimetry and polarised light microscopy. The results showed that NC forms a lyotropic liquid crystal structure in DMA. A transition from the liquid crystal phase to an isotropic phase occurred over the temperature range 27 °C to 67 °C, and the enthalpy of transition increased with NC concentration. Rheological properties were determined using an extrusion rheometer with a slit die. The solutions were shown to have a yield stress for flow which increased with increasing NC concentration. The solutions were also found to be thixotropic.     

Further study of Saint-Venant's principle in linear viscoelasticity

Summary For a viscoelastic beam loaded at one end and otherwise traction-free, it is shown that a certain integral measure of the strain in that portion of the beam at a distance greater than or equal tos decays exponentially with increasings. This is a different integral decay estimate from that obtained previously by Edelstein [2] and leads immediately to a pointwise decay estimate for strains.

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Zusammenfassung Für einen viskoelastischen Balken, der am einen Ende belastet ist, wird gezeigt, dass ein gewisses Integralmass der Verzerrung in Entfernungen, die grösser oder gleichs sind, mit zunehmendems exponentiell abnimmt. Es handelt sich dabei um eine andere Integral-Abschätzung, als sie früher von Edelstein [2] aufgestellt wurde. Sie führt direkt zu einer punktweisen Abschätzung für die Verzerrungen.

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Submitted by R.E.N. as a partial fulfillment of the requirements for the Ph.D. degree at Illinois Institute of Technology, Chicago, Illinois 60616.     

Strings with dimension-dependent intercept

By changing the boundary conditions of the relativistics string in extra dimensions, the intercept α(0) is lowered to $\text{1 ?}\text{1}\text{16}\text{(26 ?D}{}_0\text{)}$ in the modified orbital model, where D₀ is the dimensionality of the Poincaré-invariant subspace of space-time. In the modified model of the spinning string, the boson intercept becomes $\text{1}\text{2}\text{?}\text{1}\text{8}\text{(10 ? D}{}_{\mathrm{o}}\text{)}$, while the fermion intercept stays at zero. The projective invariance of the ground state is broken, giving the “photon” mass by a Higgs-like mechanism. Unfortunately, the strings have a negative “G parity”, so the usual, unshifted strings appear as intermediate states in the scattering amplitudes. Also, some of the amplitudes are not dual.     

Compactness in fuzzy topological spaces

Since earlier approaches to compactness in fuzzy spaces have serious limitations, we propose a new definition of fuzzy space compactness. In doing so, we observe that it is possible to have degrees of compactness, which we call α-compactness (α a member of a designated lattice). We obtain a Tychonoff Theorem for an arbitrary product of α-compact fuzzy spaces and a 1-point compactification. We prove that the fuzzy unit interval is α-compact.