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Bromoallenes as allyl dication equivalents in the presence or absence of palladium(0): direct construction of bicyclic sulfamides containing five- to eight-membered rings by tandem cyclization of bromoallenes.

A highly regioselective synthesis of bicyclic sulfamides is described. Based on our recent discovery that bromoallenes can act as allyl dication equivalents in the presence of a palladium catalyst and alcohol, we investigated tandem cyclization of bromoallenes bearing a sulfamide group. It is found that some bromoallenes act as allyl dication equivalents even in the absence of a palladium(0) catalyst to afford cyclosulfamides containing five- or six-membered rings. While the palladium-free cyclization is dependent on the substrate structure affording the bicyclic sulfamides through the first cyclization onto the proximal or central carbon atom of the bromoallenes, the palladium-catalyzed reaction strongly promotes the first cyclization onto the central allenic carbon atom to afford bicyclic sulfamides containing a seven- or eight-membered ring. Formation of two types of bicyclic sulfamides from single bromoallenes by simply changing the reaction conditions is also described.

Alkadienes↗

[Investigations of carbromal metabolism (author's transl)].

Erythro-2-Brom-2-ethyl-3-hydroxybutyramide has been isolated from the urines of patients with Carbromal intoxications as well as from the urine of rat, mouse and dog treated with either Carbromal or with 2-Brom-2-ethyl-acetamide. The identification of the excreted and synthetized metabolite was carried out by means of IR, Mass and NMR spectroscopy. Along with the erythro-2-Brom-2-ethyl-3-hydroxybutyramide one other bromine containing compound was isolated after Carbromal application only, its mass spectrum and rel. RF values having the same characteristics as the synthetized erythro-2-Brom-2-ethyl-3-hydroxybutyrylcarbamide. However, the purification of this metabolite so far has not been successful.

Animals↗

The detection of formaldehyde in textiles using interdigitated microelectrode array diffusion layer titration with electrogenerated hypobromite.

An interdigitated microelectrode array (IDA) was applied to the determination of formaldehyde released from textiles produced in industry. The proposed method is based on formaldehyde reaction with hypobromite which is formed in weakly basic media by control current electrooxidation of bromide on the generator segment of the IDA array. The unreacted hypobromite diffuses through the gap between individually polarisable IDA segments and it is amperometrically detected on the collector segment of the IDA. The efficiency of this nonconvective transfer process in the absence of formaldehyde was substantially higher (78%) in comparison with that when using the rotating ring disc electrode. The influence of the added formaldehyde on the transfer process can be utilised to develop a simple and sensitive analytical procedure for formaldehyde detection with a detection limit of 4 x 10(-6) mol dm(-3).

Bromine Compounds↗