Photocyclization reactions. Part 4 . Synthesis of naphtho[1,8-bc]-furans and cyclohepta[cd]benzofurans using photocyclization of Ethyl 2-(8-Oxo-5,6,7,8-tetrahydro-1-naphthyloxy)acetates and ethyl 2-(5-Oxo-6,7,8,9-tetrahydro-5H-benzocyclohepten-4-yloxy)acetates

Photocyclization reactions were carried out on ethyl 2-(8-oxo-5,6,7,8-tetrahydro-1-naphthyloxy)acetates 1a-e and ethyl 2-(5-oxo-6,7,8,9-tetrahydro-5H-benzocyclohepten-4-yloxy)acetates 2a-e in acetonitrile. Irradiation of 1a-e gave naphtho[1,8-bc]furanols 3a-e and naphtho[1,8-bc]furans 4a-e in 33–83% yields and ethyl acrylates 5b-d were produced in 3–25% yields during irradiation of 1b-d . On the other hand, 2a-e afforded cyclohepta[ad|benzofuranols 6a-e and cyclohepta[ad]benzofurans 7a-e in 44–87% yields. Ethyl acrylates 8b-d were also produced in 7–43% yields from irradiation of 2b-d . Substituent effects on photocyclization and reaction pathways are discussed.     

The family of D-weights for a two-rooted graph

Let Π(G) be the set of paths of a particular class Π from the initial to the terminal root of a two-rooted (possibly directed) graph G. We consider the family of $\text{D}$-weights defined by

where Π_x(G) is the family of subsets of Π(G) which cover x(G), the vertex set or the edge (arc) set of G.A number of the common properties and interrelations of these weights are discussed. Some of the weights have been considered previously, [1, 2], in the context of percolation theory but here only combinatorial arguments are used.     

Minor Alicyclic Diterpene Acidsfrom Conyza incana

Summary.  The reinvestigation of the CH₂Cl₂ extract of the aerial parts of Conyza incana led to the isolation of three minor alicyclic diterpene acids. The structures of the new compounds were established by a combination of spectroscopic methods. Received February 20, 2001. Accepted (revised) March 27, 2001     

Water Storage in Thin Films Maintaining the Total Film Thickness as Probed with in situ Neutron Reflectivity

We investigate a new type of thin film material which allows for water storage without an increase in film thickness, whereas typically water storage in polymers and polymer films is accompanied with a strong swelling of the film, i.e., a strong increase in the film thickness. So these films will avoid problems related to strains which are caused by swelling. The basic key for the preparation of such thin films is the installation of a glassy network by the use of an asymmetric diblock copolymer polystyrene‐block‐poly(N‐isopropylacrylamide) [P(S‐b‐NIPAM)] with a long PS and short PNIPAM block in combination with a solvent which is more equal in interaction with both the blocks as compared to water. With in situ neutron reflectivity the water storage and removal are probed. The total film thickness increases only by 2.5% by allowing for a total water storage of 17.4%. Thus the material can be used for coatings to reduce humidity in nano‐applications, which might suffer from changes in the water content of the surrounding environment.

     

The spray characteristics of a pressure-swirl injector with various exit plane tilts

The gasoline spray characteristics of a pressure-swirl injector were investigated with various exit plane tilts. The analysis focused on the correlation between tilt angle and flow angle. Mie-scattering technique and phase Doppler anemometry were employed to analyze the macroscopic spray development and droplet size distribution of the spray. An analytical method for mass flux estimation was applied to understand the velocity distribution at the nozzle exit. The results showed that the spray shape and velocity distribution of the spray were more asymmetrical at high tilt angles. In particular, an opened hollow cone spray was formed when the tilt angle is greater than the complementary flow angle. The pressure drop inside the spray, one of the crucial factors for the swirl spray collapse at various surrounding conditions, was attenuated in this opened hollow cone spray since the pressure inside the spray was assimilated to the surrounding air pressure. The spray collapse at high fuel temperature and back pressure conditions did not appear when the tilt angle is larger than the complementary flow angle due to the reduced pressure drop inside the spray. However, tilt angle should be optimized to fulfill the requirements of spray robustness and avoid the locally rich area. The droplet size of 70° tilted nozzle spray shows a value similar to that of the original swirl spray in the plane that includes nozzle axis and the major axis of exit surface ellipse (Major axis plane) while it shows an increased value in the plane that includes nozzle axis and the minor axis of exit surface ellipse (Minor axis plane).     

Partial difference equation method for lattice path problems

Many problems concerning lattice paths, especially on the square lattice have been exactly solved. For a single path, many methods exist that allow exact calculation regardless of whether the path inhabits a strip, a semi-infinite space or infinite space, or perhaps interacts with the walls. It has been shown that a transfer matrix method using the Bethe Ansatz allows for the calculation of the partition function for many non-intersecting paths interacting with a wall. This problem can also be considered using the Gessel-Viennot methodology. In a concurrent development, two non-intersecting paths interacting with a wall have been examined in semi-infinite space using a set of partial difference equations.Here, we review thispartial difference equation method for the case of one path in a half plane. We then demonstrate that the answer for arbitrary numbers of non-intersecting paths interacting with a wall can be obtained using this method. One reason for doing this is its pedagogical value in showing its ease of use compared to the transfer matrix method. The solution is expressed in a new form as a constant term formula, which is readily evaluated. More importantly, it is the natural method that generalizes easily to many intersecting paths where there is inter-path interactions (e.g., osculating lattice paths). We discuss the relationship of the partial difference equation method to the transfer matrix method and their solution via a Bethe Ansatz.     

New Polymer Syntheses Part 60: A Facile Synthetic Route to Polyamides Based on Thieno[2,3-<Emphasis Type="Italic">b</Emphasis>]thiophene and Their Corrosion Inhibition Behavior

Polyamides containing thieno[2,3-b]thiophene moiety were prepared via a simple polycondensation reaction of the diaminothieno[2,3-b]thiophene monomer 1a with different kinds of diacid chlorides (including oxalyl, adipoyl, sebacoyl, isophthaloyl, terephthaloyl, 4,4′-azodibenzoyl, 3,3′-azodibenzoyl, p-phenylene diacryloyl) in the presence of LiCl and NMP as a solvent through lowtemperature solution polycondensation. The chemical structures of model compound and synthesized polyamides were confirmed by FTIR, nuclear magnetic resonance spectroscopy (including ¹H-NMR and ¹³C-NMR) and elemental analysis. In addition, the thermal stability, crystallinity structure and surface morphology of synthesized polyamides were characterized via thermogravametric analysis (TGA), wide-angle X-ray diffraction analysis (WAXD) and scanning electron microscopy (SEM). Also, the corrosion inhibition behavior of selected examples of polyamides was investigated; the inhibitive effect of the investigated polymers for carbon steel in 1.0 mol·L^?1 HCl was studied using potentiodynamic polarization (PDP) and electrochemical impedance spectroscopy (EIS) methods. PDP results displayed that the polyamides containing thieno[2,3-b]thiophene moiety can be as mixed-type inhibitors. The inhibition efficiency (P, %) was found to be in the range from 67.13% to 96.01%. There is an increase in P by the synthesized polymers in comparison to the starting monomer. The adsorption of these polymers was found to obey Langmuir adsorption isotherm.     

Novel Dispersion of MWCNTs in Polystyrene Polymer Induced by the Addition of 3-Hydroxy-2-Napthoic Acid

This article reports an extensive investigation of the unique dispersion behavior of solutions with multi-walled carbon nanotubes (MWCNTs) and 3-hydroxy-2-napthoic acid (β-HNA) in tetrahydrofuran (THF) solvent, which results into a multifold enhancement in the electrical properties of polystyrene (PS). A number of solutions with 0.4% of MWCNTs (w/v) and β-HNA (0–1%, w/v) in THF were prepared separately. MWCNTs precipitated out in THF solvent shortly after the preparation and formed two distinct phase regions (2φ). Gratifyingly, addition of β-HNA solution to the MWCNTs solution offered an unprecedented enhancement in the dispersion of MWCNTs. Such dispersion in solutions with only 0.02% β-HNA (w/v) was found to be stable up to 2 weeks at room temperature. FTIR spectroscopy was incorporated to illustrate the adsorption of β-HNA onto the surface of carbon nanotubes (CNTs). After this successful dispersion, nanocomposites solutions comprising of 0.067% β-HNA (w/v), 6.7% PS (w/v), and varying concentrations of MWCNTs (0–0.33%, w/v) were prepared. A remarkable dispersion behavior of MWCNTs in the presence of polymer was also observed. Finally, thin films made up of consistent polystyrene/β-HNA concentrations and increasing amounts of MWCNTs were prepared by casting technique to investigate the influence of dispersion on the electrical properties of the film. The dispersion significantly affected the DC electrical conductivity and incorporation of 5% MWCNTs elevated the electrical conductivity up to 10 orders of magnitude with respect to neat PS.     

Comparative study of thermal stability and crystallization kinetics of 70B2O3-30Bi2O3 and 70B2O3-30PbO glasses

Glasses with compositions 70B₂O₃-30Bi₂O₃ and 70B₂O₃-30PbO have been prepared and studied by differential thermal analysis (DTA). The crystallization kinetics of the glasses were investigated under non-isothermal conditions. From the dependence of glass-transition temperature (T_g) on heating rate, the activation energy for the glass transition was derived. Similarly the activation energy of the crystallization process was determined. Thermal stability of these glasses were achieved in terms of the characteristic temperatures, such as glass-transition temperature, T_g, onset temperature of crystallization, T_in, temperature corresponding to the maximum crystallization rate, T_p, beside the kinetic parameters, K(T_g) and K(T_p). The results revealed that 70B₂O₃-30PbO is more stable than 70B₂O₃-30Bi₂O₃. The crystallization mechanism is characterized for both 70B₂O₃-30Bi₂O₃ and 70B₂O₃-30PbO glasses (kinetic exponent n=2.06 for 70B₂O₃-30Bi₂O₃, and n=3.03 for 70B₂O₃-30PbO). The phases at which the glass crystallizes after the thermal process were identified by X-ray diffraction.     

Simple and Clean Procedure for Three‐Component Syntheses of Spiro{pyrido[2,1‐b]benzothiazole‐3,3′‐indolines} and Spiro{thiazolo[3,2‐a]pyridine‐7,3′‐indolines} in Aqueous Medium

A simple and efficient one‐pot three component synthesis of spiro{pyrido[2,1‐b]benzothiazole‐3,3′‐indoline} and/or spiro{thiazolo[3,2‐a]pyridine‐7,3′‐indoline} derivatives were carried out by the reaction of 2‐mercaptoaniline and/or mercaptoacetic acid, malononitrile, and a series of 2‐oxoindoline‐3‐ylidines in aqueous medium. This method is of great value because of its environmentally benign character, high yield processing, and easy handling.