Stable simple enols. Resolution of chiral 1-[9'-(2'-fluoroanthryl)]-2,2-dimesitylethenol. A different racemization mechanism for the enol and its acetate

Chiral 1-[9'-(2'-methoxyanthryl)]-2,2-dimesitylethenol (2), 1-[9'-(2'-fluoroanthryl)]-2,2-dimesitylethenol (3), and 1-[9'-(2'-fluoroanthryl)]-2,2- dimesitylvinyl acetate (4) were synthesized and their DNMR behavior in C6D5NO2 was studied. 3 and 4 were resolved on an amylose tris(3,5-dimethylphenylcarbamate) HPLC column to their enantiomers. Acetate 4 racemizes slowly in solution with DeltaG(e)(++), DeltaH(e)(++), and DeltaS(e)(++) values of 26.2, 27.6 kcal mol(-)(1), and 4.3 eu, respectively, as expected for a rotational betabeta'-2-ring flip process in a vinyl propeller and the racemization is unaffected by added TFA, Et3N, and EtOD. Although 3 racemizes almost 350 times faster, the racemization is catalyzed by TFA and shows bell-shape catalysis by Et3N and a KIE in a partially deuteriated solvent. From this and the DNMR data, it is concluded that 3 does not racemize via a rotational betabeta'-2-ring flip. Five nonflip routes are discussed for the racemization of 3, and it is concluded that only the one initiated by protonation at C1 does not contradict the experimental data. By analogy with the E/Z isomerization of the structurally related 2-(m-methoxymesityl)-1,2-dimesitylethenol 17, it is suggested that in the absence of added catalyst one or more enol molecule(s) catalyze the enantiomerization of another one. Only partial resolution was achieved for 2 and from the similarity of its behavior with that of 3, it is suggested that it racemizes by the same mechanism.     

Conformational reorganization viewed by the raman spectrum of aromatic polyesters

Analysis is made of the asymmetry of the carbonyl stretching vibration of poly(ethylene terephthalate) and poly(propylene terephthalate) as a function of annealing frrom amorphous to crystalline polymer. An apparently anomalous behavior of carbonyl band half-width as a function of density for PPT is shown to be due to this asymmetry. The results are interpreted in terms of the conformational redistribution which occurs upon annealing.     

Butler groups of arbitrary cardinality

We show that in the constructible universe, the two usual definitions of Butler groups are equivalent for groups of arbitrarily large power. We also prove that Bext²(G, T) vanishes for every torsion-free groupG and torsion groupT. Furthermore, balanced subgroups of completely decomposable groups are Butler groups. These results have been known, under CH, only for groups of cardinalities ≤ ℵ_ω. Partial support by NSF is gratefully acknowledged. Partially supported by U.S.-Israel Binational Science Foundation.     

Propellanes. Part LXXII. The structure of the 4-methyl-1,2,4-triazoline-3,5-dione adduct of the propellane lactone obtained by oxidation of biphenylene

The title compound reacts with the dienophile by attacking the face of a cyclo-hexadiene ring which is syn- to the lactone ring.     

DYE LASER INTRACAVITY ABSORPTION AS AN OPTICAL PROBE IN CONDENSED PHASE AND BIOLOGICAL SYSTEMS

Abstract— A sensitive optical method to monitor local environmental changes in biological systems is described. It utilizes the high optical amplification typical to any dye laser cavity by installing the investigated system inside the laser resonator. Very small changes in the optical density of a probe dye can be detected and related to the dye's state of aggregation or in another demonstration to its adsorption on differently charged micelles and liposomes. When further developed, this technique can prove to be a very sensitive method to measure membrane potentials, changes in molecular environment and molecular dynamics. The pulsed laser used is advantageous to a continuous source used in fluorescence and absorption methods reducing photodynamic damage.     

On two problems of Erdos and Hechler: New methods in singular madness

For an infinite cardinal , denotes the set of all cardinalities of nontrivial maximal almost disjoint families over .

Erdos and Hechler proved in 1973 the consistency of for a singular cardinal and asked if it was ever possible for a singular that , and also whether for every singular cardinal .

We introduce a new method for controlling for a singular and, among other new results about the structure of for singular , settle both problems affirmatively.

     

Structural requirements in chiral diphosphine-rhodium complexes—XII: Asymmetric homogeneous hydrogenation of Z-α-N-methylacetamidocinnamic acid and methyl ester catalyzed by rhodium(I) complexes of DIOP and its carbocyclic analogues

Z-α-N-methylacetamidocinnamic acid and its methyl ester were hydrogenated with rhodhim(I) complexes containing (2R, 3R)-O-2,3-isopropylidene-2,3-dihydroxy-1,4-bis(diphenylphosphino)butane (DIOP) or its carbocyclic analogues: (1R,2R)-trans-1,2-bis(diphenylphosphinomethyl)cyclobutane or (1S,2S)-trans-1,2-bis(diphenylphosphinomethyl) cyclohexane. The N-acetyl-N-methylphenylalanine methyl ester reaction product was formed with an optical purity of 73% ee-(R) [(2R, 3R)-DIOP]; 43% ee-(R) [(1R, 2R)-cyclobutane analogue]; and 26% ee-(R) [(1S,2S])-cyclohexane analogue]. Similarly, N-acetyl-N-methylphenylalanine was formed with an optical purity of 87% ee-R [(2R, 3R)-DIOP] and 68% ee-(R) [(1R, 2R)-cyclobutane analogue].     

Excited state proton transfer in reverse micelles

The aqueous phase of water/AOT reversed micelles having varying diameters was probed by a single free diffusing proton that was released form a hydrophilic photoacid molecule (2-naphthol-6,8-disulfonate). The fluorescence decay signals were reconstructed through the geminate recombination algorithm, accounting for the reversible nature of the proton-transfer reactions at the surface of the excited molecule and at the water/detergent interface. The radial diffusion of the proton inside the aqueous phase was calculated accounting for both the entropy of dilution and the total electrostatic energy of the ion pair, consisting of the pair-energy and self-energy of the ions. The analysis implied that micellar surface must be modeled with atomic resolution, assuming that the sulfono residue protrudes above the water/hydrocarbon interface by approximately 2 A. The analysis of the fluorescence decay curves implies that the molecule is located in a solvent with physical-chemical properties very similar to bulk water, except for the dielectric constant. For reversed micelles with r(max) > or = 16 A, the dielectric constant of the aqueous phase was approximately 70 and for smaller micelles, where approximately 60% of the water molecule is in contact with the van der Waals surface of the micelle, it is as low as 60. This reduction is a reflection of the increased fraction of water molecule that is in close interaction with the micelle surface.     

Propellanes. Part LXXI. Confirmation of predicted regiospecificity in Diels-Alder reactions of certain propellanes with 4-phenyl-1,2,4-triazoline-3,5-dione

Two isomeric propellane epoxides 1a and 1b containing a cyclohexadiene ring are attacked by the title dienophile as predicted, syn to the five-membered ether ring whose α-hydrogens exert less repulsion than the α-epoxy hydrogens or the epoxide oxygen, respectively, of the cyclobutane ring.