Reductive Bergman-type cyclizations of cross-conjugated enediynes to fulvene and fulvalene anions: the role of the substituent

Various cross-conjugated enediynes undergo "Bergman-type" cycloaromatizations upon reduction with potassium metal, generating anions of fulvenes and fulvalene derivatives. This new anionic cyclization is considerably more facile than the classic Bergman cyclization with linear enediynes, creating highly reactive diradicals at -78 degrees C. Not all cross-conjugated enediynes yield cyclized dianions upon reduction; some give uncyclized, Y-shaped, cross-conjugated dianions, while others apparently yield radical-anions that either dimerize or persist as monomers. One system yields both a cyclized and an uncyclized dianion. The substituents are thus shown to be a critical factor in determining the outcome of the reduction. Cyclization occurs within a specific "window of opportunity" that is governed by the substituents.     

An Ontology of Nature with Local Causality,Parallel Lives,and Many Relative Worlds

Parallel lives (PL) is an ontological model of nature in which quantum mechanics and special relativity are unified in a single universe with a single space-time. Point-like objects called lives are the only fundamental objects in this space-time, and they propagate at or below c, and interact with one another only locally at point-like events in space-time, very much like classical point particles. Lives are not alive in any sense, nor do they possess consciousness or any agency to make decisions—they are simply point objects which encode memory at events in space-time. The only causes and effects in the universe occur when lives meet locally, and thus the causal structure of interaction events in space-time is Lorentz invariant. Each life traces a continuous world-line through space-time, and experiences its own relative world, fully defined by the outcomes of past events along its world-line (never superpositions), which are encoded in its external memory. A quantum field comprises a continuum of lives throughout space-time, and familiar physical systems like particles each comprise a sub-continuum of the lives of the field. Each life carries a hidden internal memory containing a local relative wavefunction, which is a local piece of a pure universal wavefunction, but it is the relative wavefunctions in the local memories throughout space-time which are physically real in PL, and not the universal wavefunction in configuration space. Furthermore, while the universal wavefunction tracks the average behavior of the lives of a system, it fails to track their individual dynamics and trajectories. There is always a preferred separable basis, and for an irreducible physical system, each orthogonal term in this basis is a different relative world—each containing some fraction of the lives of the system. The relative wavefunctions in the lives’ internal memories govern which lives of different systems can meet during future local interactions, and thereby enforce entanglement correlations—including Bell inequality violations. These, and many other details, are explored here, but several aspects of this framework are not yet fleshed out, and work is ongoing.     

2,4-di-tert-butyl- and 2,3,4,5-tetrachloronorcaradiene

The title norcaradienes have been synthesized by low temperature photolysis and the activation parameters for their isomerization to cycloheptatrienes determined.     

Phase transfer catalysis in N-alkylation of the pharmaceutical intermediates phenothiazine and 2-chlorophenothiazine

The N-alkylation of the two title compounds was studied, utilizing phase transfer catalysis (PTC) methods. Very mild reaction conditions were developed, especially for three-carbon N-alkylation. Of special interest is the high-yield synthesis of N-(3-chloropropyl)-2-chlorophenothiazine. The results are discussed in terms of the classical PTC/OH⁻ mechanisms.     

Anions and Polyanions of Oligoindenopyrenes: Modes of Electron Delocalization and Dimerization

A series of pyrene‐based polycyclic aromatic compounds, indeno[cd]pyrene, diindeno[cd,fg]pyrene, diindeno[cd,jk]pyrene, tris‐(tert‐butylindeno[cd,fg,jk])pyrene, and tetrakis‐(tert‐butylindeno[cd,fg,jk,mn])pyrene, were reduced with alkali metals in [D₈]tetrahydrofuran, and the resulting anions were studied by NMR spectroscopy. It was found that the diatropic character of the dianions obtained depends on the number of annulated indeno groups. When one such group is present, a paratropic dianion is obtained, which is similar to the dianion of the parent pyrene; the effect, however, is weak. When more indeno groups are annulated, the dianions become diatropic owing to the greater number of five‐membered rings that can acquire aromatic character as a result of reduction. The ¹H NMR chemical shifts of tetrakis‐(tert‐butylindeno[cd,fg,jk,mn])pyrene in the neutral state show an interesting dependence on concentration that reflects an association of the molecules in solution by π stacking. This phenomenon was not observed for the reduced species. The trianion radicals of tris‐(tert‐butylindeno[cd,fg,jk])pyrene and tetrakis‐(tert‐butylindeno[cd,fg,jk,mn])pyrene undergo reductive dimerization and form bilayered hexaanions.     

Additivity of proton and carbon nmr chemical shifts in protonated benzene carboxylic acids

The additivity of the proton and carbon chemical shift increments due to structural changes in a series of conjugate acids derived from benzene polycarboxylic acids is reported. In the acids, two sets of increments had been applied, one to the ortho diacids and one to acids which do not bear ortho substituents. In the conjugate acids only one set of increments is required. The disappearance of the ‘ortho’ effect may be the outcome of properties inherent to these conjugate acids.     

Isomerizations of benzannelated C9H10 bicyclic systems into cyclononatetraenes. insight into the behaviour of medium-sized conjugated rings

Dibenzobicyclo[5.2.0]non-8-ene 9 was prepared from 2,3:6,7-dibenzocycloheptatriene as starting material. The bicyclic system 9 isomerized thermally to give cis,trans- and cis,cis-1,2:7,8-dibenzocyclononatetraene. The formation of cis,trans-1,2:7,8-dibenzocyclononatetraene occurs in an allowed concerted electrocyclic process of general interest.     

Facile Debromination by Potassium-Graphite Intercalate

The dehalogenation of vic-dihalides can be performed with the easily accessible potassium-graphite intercalate C₈K. The reaction is a convenient one, the yields are good, and the workup us simple.