α,β-unsaturated oximes : Isoxazoline formation by thermal cyclisation of compounds related to benzalacetophenone oxime and isoxazoline thermal cycloreversion reactions

At about 300° the title compounds yield fragments attributed to cyclisation to isoxazolines and subsequent cycloreversion. Isoxazolines are formed at about 200° and can usually be isolated. At 300° they yield the same products as the oximes.Thus benzalacetophenone oxime gives 3,5-diphenylisoxazoline which then largely undergoes two distinct cycloreversions: (a) 1,3-cleavage (numbers refer to isoxazoline bonds) yielding benzonitrile and acetophenone and (b) reductive 1,4-cleavage yielding benzaldehyde and 1-phenylethylimine hydrolysis products. By-products are 2,4,6-triphenylpyridine, water and ammonium benzoate. With α-methylchalcone oxime reductive 1,4-cleavage is suppressed and with β-methylchalcone oxime both modes of cleavage are suppressed and 5-methyl-3,5-diphenylisoxazole is the stable product. An analogue of α-methylchalcone oxime, 2-methyl-1-phenyl-3-(2-thienyl)prop-2-ene-1-one oxime gives fragments attributed to both cleavage modes of an unisolatable and hitherto unknown isoxazoline.Possible mechanisms for the cyclisation and cycloreversions are discussed and the reductive 1,4-cleavage is believed to be a cycloreversion of a vinyl-nitrene.     

The E1 and E2 strength in the electrofission of some heavy elements

Measurements of the electrofission cross section for ²³²Th, ²³⁸U and ²³⁷Np have been made for an electron energy range from 20 to 120 MeV. A comparison is made between the electrofission and photofission cross sections using the concept of virtual photons. It is deduced that the electrofission reaction for these elements proceeds through a significant E2 contribution as well as an E1 transition mode.     

Reactions of unsaturated acid halides—IV: Competitive friedel-crafts acylations and alkylations of monohalogenobenzenes by the bifunctional cinnamoyl chloride

Aluminium chloride-catalysed acylations and alkylations of monohalogenobenzenes with cinnamoyl chloride has been studied. Under strictly homogeneous conditions, alkylation was increasingly favoured relative to acylation as the primary reaction along the series: benzene <fluorobenzene<bromobenzene<chlorobenzene. Changing to heterogeneous conditions (excess catalyst with CS₂ as diluent) preserved this order but primary alkylation was relatively enhanced. The addition of nitrobenzene to the homogeneous reaction restrained alkylation more than acylation.Primary acylation may be followed by alkylation giving asymmetrical 1,3,3-triarylpropan-1-ones but the possibility that these are formed by alkylation followed by acylation is ruled out. These ketones may subsequently undergo α,β-ketonic fission.Primary alkylation may be followed by cycliacylation producing 3-arylindan-l-ones with the halogeno substituent at the side-chain aryl group and this observation rules out their alternative mode of formation, cyclialkylation of the primary acylation product.An example of a para → meta bromine shift is discussed.     

Mechanism of copper underpotential deposition at Pt(<Emphasis Type="Italic">hkl</Emphasis>)-electrodes: Quantum-chemical modelling

Mechanism of copper underpotential deposition at stepped faces of platinum single crystals Pt(hkl) is studied using cyclic voltammetry, scanning probe microscopy, and quantum-chemical modelling. It is shown that the first stage of UPD is one-dimensional decoration of the (100)- or (110)-orientated steps, then copper monolayer forms at (111)-terraces. The final stage is the secondary step decoration. Quantum-chemical modelling, with the using of long-distance potentials of the Cu-Pt and Cu-Cu pair interactions, allows estimating the energy of copper adsorption at different structure elements of the substrate (steps, kinks, terraces) and revealing the succession of the adatom monolayer formation; it also provides additional information for the identifying of the nature of voltametric peaks for different stages of the copper adsorption-desorption.