From dipivaloylketene to tetraoxaadamantanes
Dipivaloylketene (2) is obtained by flash vacuum pyrolysis of furan-2,3-dione 6 and dimerizes to 1,3-dioxin-4-one 3, which is a stable but reactive ketene. The transannular addition and rearrangement of enols formed by the addition of nucleophiles to the ketene function in 3 generates axially chiral 2,6,9-trioxabicyclo[3.3.1]nonadienes (bisdioxines) 4. When arylamines are used as the nucleophiles under neutral conditions, decarboxylation occurs during the formation of bisdioxines 8. However, when water or alcohols are added to 3 under acidic conditions, bisdioxine-carboxylic acids and esters 10 and 11 are obtained. Acid hydrolysis of the bisdioxines proceeds through the addition of water to a C=C double bond and results in a second transannular oxa-Michael-type reaction and generation of tetraoxaadamantanes 5. This reaction is decarboxylative when free carboxylic acid functions are present in the bisdioxines, thus forming 21 and 22, but carboxylic acid derivatives are preserved to yield compounds 20, 23, 25, 28, and 29. A hydrogenolysis of the dibenzyl ester 23 yields the free dicarboxylic acid 24. The tetraoxaadamantanes are formed in high yields (65–95%) in most cases, but the addition of water to the concave inside of the bisdioxines becomes severely hindered in cyclic derivatives, so that the 38-membered ring compound 32 requires microwave heating at 170 °C to form tetraoxaadamantane 33, and the catenated compound 36 and calix[6]arene derivative 37 did not form tetraoxaadamantanes. The reaction mechanisms of bisdioxine and tetraoxaadamantane formation are discussed.
Acyl(imidoyl)ketenes: Reactive Bidentate Oxa/Aza-Dienes for Organic Synthesis
Polyfunctional building blocks are essential for the implementation of diversity-oriented synthetic strategies, highly demanded in small molecule libraries’ design for modern drug discovery. Acyl(imidoyl)ketenes are highly reactive organic compounds, bearing both oxa- and aza-diene moieties, conjugated symmetrically to the ketene fragment, enabling synthesis of various skeletally diverse heterocycles on their basis. The highlights of reactions utilizing acyl(imidoyl)ketenes are high yields, short reaction time (about several minutes), high selectivity, atom economy, and simple purification procedures, which benefits the drug discovery. The present review focuses on the approaches to thermal generation of acyl(imidoyl)ketenes, patterns of their immediate transformations via intra- and intermolecular reactions, including the reactions of cyclodimerization, in which either symmetric or dissymmetric heterocycles can be formed. Recent advances in investigations on mechanisms, identifications of intermediates, and chemo- and regioselectivity of reactions with participation of acyl(imidoyl)ketenes are also covered.
D'une application pratique des indices bio-météorologiques
Abstract The purpose of the author is to determine statistically in what part of Switzerland maize could be cultivated with certain chance of rentability. The author gives first the method he used for determining the biometeorological index of four species of maize which were selected by the Swiss agronomical research stations. He has considered two possibilities for the growing period: ( a ) raising-ripening (l'approche globale); ( b ) raising-flowering, flowering-ripening (l'approche fractionee). From the biometeorological index, he calculated retrospectively the ripening time of these four species in the years 1901–1965. Assuming a priori that maize should be harvested before October 15th at the latest, he calculated, for a number of meteorological stations, the relative number of years when such conditions were fulfilled. Dividing the country in regions of similar mesoclimates and sorting these stations per region, it is possible to average the maximum altitude where maize can ripen at least 7, 8, 9 and 10 times within 10 years. Finally, taking into account the exposure and ground slope, he draws maps of the theoretically possible extension area, which maps are more reliable and detailed than the ones derived from actual means.