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 ).     

Complexes in polymers IV. FTIR microscopic characterization of thin organic polymer films containing embedded transition-metal carbonyl complexes

Thin films of polystyrene (PS), poly(methyl methacrylate) (PMMA) and polystyrene-polyacrylonitrile copolymer (PS-AN), containing various embedded transition-metal complexes, have been studied by FTIR microscopy. The spatial distributions of the transition-metal carbonyl complexes throughout the thin organic polymer films have been determined by a two-dimensional IR mapping procedure. The spectral variations observed in the distribution of the metal carbonyls throughout the different polymer films are discussed. The IR data show that the technique used to prepare the organometallic-embedded thin films (viz. freeze-drying of solutions followed by hot mechanical pressing of the residues) does in general lead to homogeneous films which may eventually find industrial application, e.g. as membrane sensors for small molecules.     

Critical branching in a highly fluctuating random medium

Summary A model of one-dimensional critical branching (superprocess) is constructed in a random medium fluctuating both in time and space. The medium describes a moving system of point catalysts, and branching occurs only in the presence of these catalysts. Although the medium has an infinite overall density, the clumping features of the branching model can be exhibited by rescaling time, space, and mass by an exactly calculated scaling power which is stronger than in the constant medium case. The main technique used is the asymptotic analysis of a generalized diffusion-reaction equation in the space-time random medium, which (given the medium) prescribes the evolution of the Laplace transition functional of the Markov branching process.     

A generalization of Connor's inequality to t-designs with automorphisms

In this paper the incidence algebra for t-designs with automorphisms and the fundamental theorem discovered in [4] are exploited to obtain a generalization of Connor's inequality.     

Gravitational Entropy in Cosmological Models

We discuss whether an appropriately defined dimensionless scalar function might be an acceptable candidate for the gravitational entropy, by explicitly considering Szekeres and Bianchi type VI _h models that admit an isotropic singularity. We also briefly discuss other possible gravitational entropy functions, including an appropriate measure of the velocity dependent Bel-Robinson tensor. PACS: 04.20.-q 95.30.Sf 98.80.Jk     

A simple approximation for the vibrational partition function of a hindered internal rotation

A simple formula is presented for calculating the approximate partition function of a hindered internal rotational mode of a polyatomic molecule. The formula gives useful accuracy over the whole range from harmonic oscillator to hindered rotator to free rotator.