Reactivity of 3-alkyl-4-arylazomethylene-3,4-dihydro-1,2,3-benzotriazines in protic solvents: 1,4-Addition reactions and dimroth rearrangement

3-Alkyl-4-arylazomethylene-3,4-dihydro-1,2,3-benzotriazines 5a and 5b undergo facile 1,4-addition of methanol or ethanol to afford stable crystalline hydrazones, 6 and 8 which have been characterised by spectroscopic analysis. In particular, the nmr spectrum of 8 shows novel features due to the diastereotopic nature of the CH₂ protons in the two O-ethyl groups. Compound 5b shows a property unique to the compounds in this series; refluxing this arylazomethylenetriazine in ethanol affords a rearranged product, characterised as the 1-aryl-2-cinnolinylhydrazine ( 9 ). The formation of 9 is rationalised as a ring opening-ring closure process analogous to the Dimroth rearrangement. The cinnoline 9 displays some novel chemistry arising from the facility of the arylhydrazino substituent to react with acid to give a fragmentation product, 3-methylindazole ( 7 ).     

Many-neighbour interaction and non-locality in traffic models

The optimal-velocity model, as proposed by Bando et al. [1], shows unrealistic values of the acceleration for various optimal-velocity functions [2,3]. We discuss different approaches of how to correct this problem. Multiple look-ahead (many-neighbour interaction) models are the most promising candidates in reducing accelerations and decelerations to realistic values. We focus on two such models and, in particular, their linear stability and how these affect the vehicle dynamics and wave solutions. As found earlier [4], multiple look-ahead models reproduce many real flow features, and our results further support the necessity of this ansatz. However, the problem of non-locality arises when they are transformed into the corresponding continuum model. We discuss three methods of how to interpret many-neighbour interaction in macroscopic models.Received: 27 March 2004, Published online: 12 July 2004PACS: 45.70.Vn Granular models of complex systems; traffic flow - 89.90. + n Other topics in areas of applied and interdisciplinary physics - 47.50. + d Non-Newtonian fluid flows     

Speciation and biosynthetic variation in four dictyoceratid sponges and their cyanobacterial symbiont, Oscillatoria spongeliae

Four species of marine sponges (Phylum Porifera, Order Dictyoceratida), which contain the filamentous cyanobacterial symbiont Oscillatoria spongeliae, were collected from four locations in Palau. The halogenated natural products associated with the symbiont were characterized from each sample, revealing that each species contained either chlorinated peptides, brominated diphenyl ethers, or no halogenated compounds. Analysis of the host sponges and the symbionts indicated that each species of sponge contained a distinct strain of morphologically similar cyanobacteria. Although cospeciation may be present in this group, we have identified that at least one host switching event has occurred in this symbiosis. Only the strain of O. spongeliae in the sponge containing the chlorinated compounds possessed genes involved in the biosynthesis of chlorinated leucine precursors, indicating that the chemical variation observed in these animals has a genetic foundation.     

Analysis of ephedrine in ephedra callus by acetonitrile modified capillary zone electrophoresis

A simple method has been developed for the quantitative determination of ephedrine in ephedra callus. The dependence of effective mobility of ephedrine on pH was investigated, and a simulated equation was obtained. The separation was performed in an uncoated capillary and detected at 185 nm. A new Tris–NaOH–H₃PO₄ run buffer was used and the pH was adjusted to 3.20. To increase the solubility of hydrophobic analytes and improve the separation efficiency, 15% acetonitrile was used in the buffer as a modifier. The content of ephedrine in an ephedra callus sample and an ephedra herba sample were determined with this method, and the result was satisfactory.     

Scope and mechanism of palladium-catalyzed amination of five-membered heterocyclic halides

Detailed studies have been conducted to determine the activity of palladium catalysts for the amination of five-membered heterocyclic halides and to determine the factors that control the scope of this reaction. Palladium-catalyzed aminations of the electron-rich furanyl, thiophenyl, and indolyl halides and of the related 2-halogenated thiazoles, benzimidazole, and benzoxazole have been shown to occur with a subset of amines. Various combinations of palladium precursors and P(t)Bu(3) were tested as catalysts for reaction of 3-bromothiophene with N-methylaniline, and the fastest reactions occurred with the Pd(I) dimer, [PdBr(P(t)Bu(3))](2). The fastest aminations of thiazoles, benzimidazoles, and benzoxazoles occurred with the combination of palladium trifluoroacetate and P(t)Bu(3) as catalyst.     

Cationic copolymerization of tetrahydrofuran with epoxides. III. Synthesis of block copolymers

Polymerization of various cyclic ethers by BF₃·O(C₂H₅)₂ in the presence of polymeric glycol leads to the formation of hydroxyl terminated block copolymers. Where poly(oxyethylene glycol) is used as the polymeric glycol, fission of the poly(oxyethylene glycol) chain occurs, and block copolymers, containing shorter ethylene oxide unit sequences are obtained. With poly(oxypropylene glycol), on the other hand, the polymer chain remains intact. This may be due to the steric influence of the pendant methyl groups. The cyclic oligomers formed as by-products in the polymerizations are easily removed.     

Novel siloxane polymers as polymer electrolytes for high energy density lithium batteries

A variety of disubstituted (double-comb) polysiloxane polymers have been prepared containing linear, branched, and cyclic oligoethyleneoxide units, –(OCH₂CH₂)_n–, in the side chains and as part of the siloxane backbone. Copolymers, using mixtures of linear ethylene oxide side chains, were also synthesized. These polymers were doped with LiN(SO₂CF₃)₂ (LiTFSI, 1) and conductivities of the polymer-salt complexes were determined as a function of temperature and doping level. The maximum conductivity of these polymers at 25 ° C was 2.99 ×10^–4, for a copolymer containing equimolar amounts of side chains with n = 5 and 6.     

Bimetallic Gold(I) Complexes with Ethynyl‐Helicene and Bis‐Phosphole Ligands: Understanding the Role of Aurophilic Interactions in their Chiroptical Properties

Monometallic gold(I)‐alkynyl‐helicene complexes ( 1 a , b ) and bimetallic gold(I)‐alkynyl‐helicene architectures featuring the presence ( 2 a , b ) or absence ( 3 a , b ) of aurophilic intramolecular interactions were prepared by using different types of phosphole ligands (mono‐phosphole L1 or bis‐phospholes L2 , 3 ). The influence of the Au^I d¹⁰ metal center(s) on the electronic, photophysical, and chiroptical properties of these unprecedented phosphole‐gold(I)‐alkynyl‐helicene complexes was examined. Experimental and theoretical results highlight the importance of ligand‐to‐ligand‐type charge transfers and the strong effect of the presence or absence of Au^I–Au^I interactions in 2 a , b .     

Large‐Scale Synthesis of Helicene‐Like Molecules for the Design of Enantiopure Thin Films with Strong Chiroptical Activity

Helicenes are fascinating molecules owing to their unusual properties and applications in many fields from catalysis to organic electronics. Herein, we report a straightforward pathway for the synthesis of helicene‐like molecules on a gram scale in an enantiopure form. Thin‐film materials with good propagating optical properties and very high chiroptical responses have been grown by using pulsed laser ablation without altering the structure or the enantiopurity of the molecules. Moreover, electronic and vibrational circular dichroism spectroscopies coupled with theoretical calculations enabled some dependences of the chiroptical properties with the structure to be highlighted, for example, effects of rigidification, aromatization, or the state of matter (liquid versus solid).