1,3-bis(diarylmethylidene)-2-methylidenecyclohexanes in cycloaddition and cyclodimerization reactions. The role of stereoelectronic factors.
Cycloaddition and cyclodimerization reactions of 1,3-dibenzylidene- and 1,3-bis(p-methoxybenzylidene)-2-methylidenecyclohexanes, i.e., the diaryltrienes with fixed S-cis-configurations of exocyclic double bonds are studied. These compounds undergo in situ cyclodimerization of the [4 + 2]-type upon dehydration of the precursor tertiary alcohols and form endo-adducts in the Diels-Alder reaction with N-phenylmaleimide. In the presence of CF3COOH, acid-catalyzed cyclodimerization takes place leading to methylidene-substituted spirocyclodimers, which undergo intramolecular cyclization upon prolonged contact with CF3COOH to form a fused carbocyclic system containing a central, 'three-petal' fragment of six-membered rings.
Cyclodimerization of the 1-methyl-1,3-diferrocenylallyl cation into 1,3,5-triferrocenyl-4-(1-ferrocenylethenyl)cyclohexene
An unusual cyclodimerization reaction of the 1-methyl-1,3-diferrocenylallyl cation into 1,3,5-triferrocenyl-4-(1-ferrocenylethenyl)cyclohexene has been studied. Two isomeric compounds were isolated and their structures were established as 1,r3,c5-triferrocenyl-4-t-(1-ferrocenylethenyl)cyclohexene and 1,r3, t5-triferrocenyl-4-c-(1-ferrocenylethenyl)cyclohexene on the basis of 1H NMR and 13C NMR spectral data.
Control of the homopause level
Abstract This paper reviews the hypothesis that internal gravity wave breaking in the factor responsible for upper atmosphere turbulence generation and control of the number density at the homopause level. Available data from Mars and Earth support the hypothesis, originally introduced by Lindzen, that breaking thermal tides are responsible for the necessary turbulence. The lowest-order, equatorially trapped, westward-propagating diurnal tidal mode is the primary cause on the Earth, and lower-order westward-propagating semidiurnal modes are the primary cause on Mars. The frequencies and vertical wavenumbers of the responsible modes determine the eddy diffusion coefficients; energy density is only indirectly involved by determining which modes can break. A general scale relationship between tidal heating and velocity amplitude can be used to assess the breaking potential of tidal modes, and is used here as the basis for arguing that the number density at the Martian homopause is likely to have been stable over much of geologic time. Difficulties with this approach arise in the cases of Venus and Titan because of their peculiar zonal winds. For Jupiter and Saturn, internal gravity waves generated by nontidal mechanisms probably control the homopause.