Pyridines from azabicyclo[3.2.0]hept-2-en-4-ones through a proposed azacyclopentadienone

Pyridines have been formed by heating azabicyclo[3.2.0]hept-2-en-4-ones in toluene. The generation of a 3-azacyclopentadienone intermediate via a [2 + 2]-cycloreversion is proposed as the key step. A Diels-Alder reaction of a styrene, extrusion of carbon monoxide, and loss of hydrogen then gives the pyridine. The process parallels the well-known synthesis of benzenes from cyclopentadienones. The azabicyclo[3.2.0]hept-2-en-4-ones were synthesized from the reaction between readily available cyclopropenones and 1-azetines, in which the cyclopropenones behave as all-carbon 1,3-dipolar equivalents.     

Assessments accompanying published textbooks: the extent to which mathematical processes are evident

Assessments accompanying published textbooks are often used by teachers in the USA as a primary means to evaluate students’ mathematical knowledge. In addition to assessing content knowledge, assessments should provide insight into students’ ability to engage with mathematical processes such as reasoning, communication, connections, and representations. We report here an analysis of the extent to which the assessments accompanying published textbooks in the USA at the elementary, middle grades, and high school levels provide opportunities for students to engage with these mathematical processes. Results indicate that in elementary grades, communication, connections, and graphics are not consistently emphasized across grade levels and publishers. In middle grades, students are rarely asked to record their reasoning or translate among representational forms of a concept. In high school geometry, students are given many opportunities to interpret and create graphics, but the same is not true for algebra. With the exception of connections, the results suggest that inconsistent emphasis is placed on the mathematical processes within assessments accompanying commercial textbooks in the USA.     

Influence of clay modification on the properties of aramid-layered silicate nanocomposites

Nanocomposites from organoclay and aromatic polyamide were prepared using solution intercalation method. Aramid chains were synthesised by reacting 4-aminophenylsulfone with isophthaloyl chloride in dimethylacetamide. Dodecylamine was used as a modifier to change the hydrophilic nature of montmorillonite into organophilic. Suitable quantities of organoclay were mixed in the aramid solution with high-speed stirring for homogeneous dispersion of the clay. Thin films cast from these materials after evaporating the solvent were characterised. The morphology of nanocomposites was determined by X-ray diffraction and TEM. Results revealed the formation of delaminated and disordered intercalated clay platelets in the aramid matrix. Mechanical data indicated improvement in the tensile strength and modulus with clay loading up to 6 wt.%. The glass transition temperature increased up to 20 wt.% organoclay, suggesting better cohesion between the two phases and thermal stability augmented with increasing clay loading. The water uptake reduced gradually as a function of organoclay showing decreased permeability.     

Methane hydrate phase equilibrium in the presence of NaBr,KBr, CaBr2, K2CO3, and MgCl2 aqueous solutions: Experimental measurements and predictions of dissociation conditions

In this communication, experimental data for dissociation conditions of methane hydrates in the presence of 0.05 and 0.1 mass fractions NaBr, KBr, K₂CO₃, and MgCl₂ aqueous solutions and in the presence of 0.05 and 0.15 mass fractions CaBr₂ aqueous solutions are reported. The experimental data were generated using an isochoric pressure-search method. The new experimental dissociation data for methane hydrates in the presence of 0.1 mass fraction MgCl₂ aqueous solution are compared with some selected experimental data from the literature and the agreements are generally found acceptable. Some of new data are finally compared with the predictions of a correlation, which is generally used in the absence of experimental data, and acceptable agreements between the experimental and predicted data are observed.     

Empirical relationship for humidity and temperature at Quetta, Pakistan

A Gaussian trend for humidity versus temperature is confirmed by a theoretical fit, i.e., 

where T₀ and H₀ are the experimental values of the temperature and humidity, respectively and K is a constant.     

Epoxidations by peracid anions in water: ambiphilic oxenoid reactivity and stereoselectivity

[reaction: see text] Transition structures have been located for oxygen transfer from performate anion to ethylene, propene, vinylamine, vinyl chloride, vinyl cyanide, and 2-propen-1-ol at the B3LYP/6-31+G(d,p) level in a CPCM continuum model for water. Oxygen transfer is concerted, except for acrylonitrile, which is stepwise. Peracid anions react as ambiphilic oxygen donors. Predictions are made about the diastereoselectivity of epoxidations of acylic, chiral, and allylic alcohols in an alkaline solution, and one is verified experimentally.     

N-aminopyrroledione-hydrazonoketene-pyrazolium oxide-pyrazolone rearrangements and pyrazolone tautomerism

Flash vacuum thermolysis (FVT) of 1-(dimethylamino)pyrrole-2,3-diones 5 causes extrusion of CO with formation of transient hydrazonoketenes 7. The transient ketenes 7 are observable in the form of weak bands at 2130 (7a) or 2115 cm-1 (7b) in the Ar matrix IR spectra resulting from either FVT or photolysis of either 5 or 1,1-dimethylpyrazolium-5-oxides 8, and these absorptions are in excellent agreement with B3LYP/6-31G* frequency calculations. Under FVT conditions the ketenes 7 cyclize to pyrazolium oxides 8, which undergo 1,4-migration of a methyl group to yield 1,4-dimethyl-3-phenylpyrazole-5(4H)-one 9a and 1,4,4-trimethyl-3- phenylpyrazole-5(4H)-one 9b. All three tautomers of 9a have been characterized, viz. the CH form 9a (most stable form in the gas phase, the solid state and solvents of low polarity), the OH form 9a' (metastable solid at room temperature) and the NH form 9a" (stable in aprotic dipolar solvents). The isomeric 1,4-dimethyl-5-phenylpyrazole-3(2H)- one 12 tautomerizes to the 3-hydroxypyrazole 12'. The crystal structure of the hydrochloride 14 of 9a'/9a" is reported, representing the first structurally characterised example of a protonated 5-hydroxypyrazole.     

An ab initio LCAO-MO-SCF study of the electronic structure of phosphirane and thiirane

Wave functions have been determined for the C₂H₄PH and C₂H₄S cyclic molecules, using (951/52/3) and (95/52/3) uncontracted Gaussian basis sets for each molecule. From Mulliken population analyses and electron-density plots, it is shown that the valence orbitals of C₂H₄PH and C₂H₄S are closely related and that these are similar to the respective orbitals of cyclopropane.

---

Zusammenfassung Für die zyklischen Moleküle C₂H₄PH und C₂H₄S wurden mit den nichtkontrahierten Basissätzen ((951/52/3) und (95/52/3)) von Gaußfunktionen Wellenfunktionen bestimmt. Die Mullikenschen Populationsanalysen sowie Diagramme der Elektronendichte zeigen, daß die Valenzorbitale von C₂H₄PH und C₂H₄S in enger Beziehung stehen und daß diese den entsprechenden Orbitalen des Cyclopropans ähnlich sind.