A High－efficiency Preparation, Properties and Structure of （R, S ）－and （ S, S）－Pyrrolidine－2－carboxylic Acid 3,5－Dioxa－4－boracvclo.hepta [ 2,1－α; 3,4－α′] dinaphthalen－4－yl Esters

A highly-efficient preparative procedure for ( R, S )- and ( S, S)-pyrroHdine-2-carboxyHc acid 3,5-dioxa-4-boracyclohepta[2, 1-α ; 3,4-α′] dlnaphthalen-4-yl esters [ namely ( R, S )-BNBAP and (S, S )-BNBAP] is described and the crystal structure of (R, S )-BNBAP was obtained. The data indicate that ( R, S )-BNBAP is a spirocyclic inner borate salt with almost normal te-trahedral configuration. This structural form may be the basic reason for their high chemical, optical and thermodynamic sta-bility.     

Extrudate swell behavior of PS and LLDPE melts in a dual die with mixed circular/slit flow channels in an extrusion rheometer

Extrudate swell behaviors of polystyrene (PS) and linear low‐density polyethylene (LLDPE) melts in a dual channel die, having mixed circular/slit flow channels, in a constant shear rate rheometer were examined. The extrudate swell ratio for PS melt was observed to be higher than that for LLDPE melt for all cases, this being associated with the differences in molecular structures that could be described in terms of power law indexes and secondary flows near the die entrance. In single channel die, the extrudate swell of both PS and LLDPE melts in circular flow channel die was greater than that in slit flow channel, whereas, in dual channel die the slit channel exhibited a higher extrudate swell ratio, the results being explained by revealing the flow patterns of the melt in the barrel and die of the rheometer. It was found that the dimensionless size of the vortex flows near the entrance, and the extent of disentanglement of molecular chains on entering the die were the important factors for the differences in the extrudate swell ratios of the melts at the die exit influenced by the die designs used. Copyright © 2003 John Wiley & Sons, Ltd.     

Selective Transport of Alkali—Metal Cations through Liquid Membranes by Non—Cyclic Carriers

The emission spectra of a series of naphthalene end-labeled oligo-oxyethylene(N-Pn-N) and their facilitated transport of cations across liquid membranes have been investigated.Alkali-metal cations enhance or inhibit the intramolecular excimer formation of N-Pn-N remarkably,suggesting that the polyether chain of N-Pn-N in solution complexes with the cations,and the orientation of the terminal chromophores depends on the cation size and the length of the polyether chain. These compounds are able to act as carriers to facilitate transport of alkali-metal cations through organic liquid membranes.The transport efficiencies are comparable with those of cyclic carriers such as crown ethers,and show remarkable selectivity.     

苯并菲盘状液晶的合成、亲氟效应及分子对称性对介晶性的影响

New symmetrical and asymmetrical triphenylene-containing discotic liquid crystals with two different peripheral alkyl chains, known as sym-TP(OC6H13)3(OR)3 and asym-TP(OC6H13)3(OR)3, were synthesized. Their thermotropic liquid crystal properties were investigated through polarizing optical microscopy (POM), differential scanning calorimetry (DSC) and X-ray diffraction (XRD) analyses. The asyrranetdcal discogens are 2,6,11-rialkoxy-3,7,10-trihexyloxytriphenylenes, with the alkyl chain carbon numbers varying from 3-10, 12, and 14, while the symmetrical compounds are 2,6,10-trialkyloxy-3,7,11-trihexyloxytriphenylene. Two fluoroalkoxy substituted triphenylene discogens, 2,6,10-td(4,4,4-trifluorobutoxy)-3,7,11-trihexyloxytriphenylene and its asymmetrical isomer 2,6,11-tri(4,4,4-trifluorobutoxy)-3,7,10-trihexyloxytdphenylene were prepared. These two compounds show higher melting and clearing points than their alkoxy analogs, which implies that fluorophilic effect exists in the formation and stabilization of discotic columnar mesophase. The triphenylene derivatives TP(OC6H13)3(OR)3 with two different peripheral chains, symmetrically or asymmetrically attached on triphenylene cores, have lower melting points and clearing points than those of the higher symmetrical compounds TP(OR)6 with the same total chain carbon numbers. The mixed-chain-triphenylenes with longer alkoxy chains (n=9,10,12,14) show columnarmesophase at room temperature.     

Design and Synthesis of 3‐Aryl‐5‐Alicylic‐[1,2,4]‐oxadiazoles as Novel Platelet Aggregation Inhibitors

A series of 4‐[2‐(alicyclic‐[1,2,4]oxadiazol‐3‐yl)phenoxy]‐butyric acids were synthesized from N‐hydroxy‐2‐isopropoxy benzamidine in 4 steps with good yields. These [1,2,4]oxadiazoles are novel platelet aggregation inhibitors preventing human platelet aggregation induced by thromboxane derivative U44,619 and adenosine diphosphate. A structure‐activity‐relationship study revealed that the potency for these 5‐oxadiazoles increases with the increase in the ring size of the alicylic rings. Derivative 8f may be useful as a template for the design of more potent anti‐platelet agents.     

Ab initio calculations and vibrational energy level fits for the lower singlet potential-energy surfaces of C3

Ab initio multireference configuration interaction potential energy surfaces are computed for the eight lowest singlet surfaces of C(3). These reveal several important features, including several conical intersections in linear, nonlinear, and equilateral triangle geometries. These intersections are important because, particularly for the excited A (1)Pi(u) state, reasonable ab initio results could only be obtained by including nearby, near degenerate, (1)Sigma(u) (-) and (1)Delta(u) states that cross the A (1)Pi(u) state around 4500 cm(-1) above the equilibrium geometry, and a (1)Pi(g) state whose potential in turn crosses the other states about 2000 cm(-1) further up. These states are probably responsible for the complexity of the shorter wavelength UV absorption spectrum of C(3). The computed potential energy surface for the ground, X (1)Sigma(g) (+), state and for the lowest two excited singlet surfaces (which both correlate with the A (1)Pi(u) state in a collinear geometry) are fitted to analytic functional forms. Vibrational energy levels are calculated for both states, taking account of the Renner-Teller coupling in the excited A (1)Pi(u) state. The potential parameters for both states are then least-squares fitted to experimental data. The ground-state fit covers a range of approximately 8500 cm(-1) above the lowest level, and reproduces 100 observed vibrational levels with an average error of 2.8 cm(-1). The A (1)Pi(u) state surfaces cover a range of 3250 cm(-1) above the zero-point level, and reproduce the 44 observed levels in this range with an average error of 2.8 cm(-1).     

The Structure of Bis[N‐6‐aminopyridyl‐N‐(1S)‐(+)‐10‐camphorsulfonylamino]palladium in the Solid State and in Solution

The complex, bis[N‐6‐aminopyridyl‐N‐(1S)‐(+)‐10‐camphorsulfonylamino]palladium, Pd[(S)‐APCS]₂, 1 , was prepared by reaction of 2‐[(1S)‐(+)‐10‐camphorsulfonamino]‐6‐aminopyridine with PdCl₂ in THF. Complex 1 has been characterized by spectroscopic methods and its structure has been determined by X‐ray crystallography. Crystal data: space group C2, a= 16.082 (2), b = 17.104 (2), c = 13.051 (2)Å, β = 99.95 (1)°, V = 3535.9 (8) ų, Z = 2 with final residuals R1 = 0.0491 and wR2 = 0.0944. Two independent molecules, (S,S)‐Pd[(S)‐APCS]2, 1a , and (R,R)‐Pd[(S)‐APCS]2, 1b , were found in each asymmetric unit, which exchange to each other via a series of nitrogen inversion and C‐C bond rotation. The inversion energy (ΔGc₁^≠) and the energy barrier (δGc₂^≠) were 11.5 ± 0.1 Kcal mol^?1 at 246 K and 9.8 ± 0.1 Kcal mol^?1 at 199 K, respectively, calculated by dynamic NMR data.     

Synthesis of New Spiropyrans With a Polyaromatic or Heteroaromatic Pendant and Their Photochromic Bedhaviors

A series of spiropyrans with a polyaromatic or heteroaromatic pendant was synthesized conveniently.Their photochromic behaviors were investigated with the aid of absorption spectral measurements.The results indicated that the compounds with the same parent spiropyran but different aromatic pendant show significantly different photochromic properties.This may be due to the π-π orbital interaction between the polyaromatic pendant and the open photomerocyanine form of spiropyran.The results obtained are very useful in the molecule design area.     

Synthesis and properties of organosoluble poly(amide imide imide)s based on tetraimide dicarboxylic acid condensed from 4,4′‐(hexafluoroisopropylidene)diphthalic anhydride, 4,4′‐oxydianiline,and trimellitic anhydride and various aromatic diamines

A novel tetraimide dicarboxylic acid was synthesized with the ring‐opening addition of 4,4′‐(hexafluoroisopropylidene)diphthalic anhydride, 4,4′‐oxydianiline, and trimellitic anhydride in a 1/2/2 molar ratio in N‐methyl‐2‐pyrrolidone followed by azeotropic condensation to tetraimide dicarboxylic acid. A series of poly(amide imide imide)s (PAIIs) with inherent viscosities of 0.8–1.1 dL/g were prepared from tetraimide dicarboxylic acid with various aromatic diamines by direct polycondensation. Most of the PAIIs were readily soluble in a variety of amide polar solvents and even in less polar m‐cresol and pyridine. Solvent‐cast films had tensile strengths ranging from 99 to 106 MPa, elongations at break ranging from 8 to 13%, and initial moduli ranging from 2.0 to 2.3 GPa. The glass‐transition temperatures of these PAIIs were recorded at 244–276 °C. They had 10% weight losses at temperatures above 520 °C in air or nitrogen atmospheres. © 2002 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 40: 1092–1102, 2002     

Total Synthesis of (+)‐β‐Himachalene

An enantioselective synthesis of (+)‐β‐himachalene ( 2 ) was accomplished starting from (1S,2R)‐1,2‐epoxy‐p‐menth‐8‐ene ( 3 ) in 15 or 16 steps with an overall yield of ca. 6% (Schemes 3, 5, and 6). Key transformations include an Ireland–Claisen rearrangement, a Corey oxidative cyclization, and a ring expansion.