Neighbouring-group Influence on the Ring Opening of Some 2-Alkyl-1,1,2-tribromocyclopropanes under Phase-transfer Conditions

Several 2-alkyl-1,1,2-tribromocyclopropanes were treated with sodium hydroxide and ethanol under phase-transfer conditions. Ring opening gave mixtures of the corresponding acetylenic diethyl ketals and acetals. When the steric bulk of the alkyl substituent was increased acetal formation dominated, and in the case of 1,1,2-tribromo-2-(tert-butyl)cyclopropane, the acetal was formed as the only product.     

Formation of tricyclo[6.3.0.02,5]undecane derivatives during attempts to make the rumphellatin A–C oxacarbon skeleton

The results of several approaches to make the 4,4,8-trimethyl-12-oxatricyclo[7.2.1.0^2,5]dodecane motif present in rumphellatins A–C are reported. The strategy adopted involved (9E)-12,12-dimethyl-5-oxatricyclo[8.2.0.0^4,6]dodec-9-en-11-ol as an intermediate, but when attempts were made to connect the third methyl group to the carbon skeleton by reacting the epoxide with MeLi under boron-trifluoride catalysis, an unprecedented transannular reaction occurred. The desired product was not formed; instead, compounds containing a tricyclo[6.3.0.0^2,5]undecane moiety were obtained, in one case in better than 70% yield.     

The Onset of Convection in an Inclined Anisotropic Porous Layer with Oblique Principle Axes

We consider the onset of convection in an inclined anisotropic porous layer heated from below. To date the principle axes of the permeability and diffusivity tensors have been assumed to be aligned with the coordinate directions. Therefore particular emphasis is laid upon how the basic flow and criteria for the onset of convection are altered by the presence of oblique principle axes. When these axes are not aligned with the coordinate directions and when the ratios of the principle permeabilities or diffusivities are not too large or too small, we find that there is always a smooth transition in the orientation of the most dangerous mode of instability as the inclination increases from the horizontal. In more extreme cases there may be sudden changes in the orientation, Darcy–Rayleigh number and wavenumber.     

The Onset of Darcy–Forchheimer Convection in Inclined Porous Layers Heated from Below

It is well known that the onset of convection in an inclined porous layer heated from below takes the form of longitudinal vortices when Darcy’s law is valid. In this paper we consider briefly how the onset criterion alters when form drag, as modelled by the Forchheimer terms, is significant. In general, the critical Rayleigh number increases substantially as form drag effects strengthen, but the wavenumber rises by only a small amount. This numerical study is supplemented by a brief asymptotic analysis of the case when the Forchheimer terms dominate and it is shown that the critical Rayleigh number increases in direct proportion with the form drag parameter.     

Synthesis of (E)‐1,1‐Diethoxy‐3‐(3‐hydroxy‐3‐arylfuro[2,3‐b]quinoxalin‐2(3H)‐ylidene)propan‐2‐ones via Acid‐Catalyzed,Stereoselective 5‐Exo‐Dig Cyclization

A number of 3‐(4,4,5,5‐tetraethoxy‐1‐hydroxy‐1‐arylpent‐2‐ynyl)quinoxalin‐2(1H)‐ones, obtained by reacting the lithium acetylide of 3,3,4,4‐tetraethoxybut‐1‐yne (TEB) with 3‐aroylquinoxalin‐2(1H)‐ones, appeared to undergo stereoselective cyclization in the 5‐exo‐Dig manner when heated at reflux in acidic, aqueous THF. In each case, the products were the corresponding (E)‐1,1‐diethoxy‐3‐(3‐hydroxy‐3‐arylfuro[2,3‐b]quinoxalin‐2(3H)‐ylidene)propan‐2‐ones and 1,1‐diethoxy‐3‐hydroxy‐3‐(3‐arylfuro[2,3‐b]quinoxalin‐2‐yl)propan‐2‐one, which were isolated in an approximate ratio of 2:1 in high total yield. Irrespective of the structure of the aryl group, both compounds were stable solids when kept in a refridgerator (3 °C), but when the latter product was dissolved in chloroform and stored at room temperature, it rearranged smoothly and quantitatively to the former compound within a few days.     

Synthesis and some chemical properties of 3,3,4,4-tetraethoxybut-1-yne

Ring opening of 1,1-dibromo-2-chloro-2-diethoxymethylcyclopropane in a mixture of ethanol and dichloromethane with 50% aqueous sodium hydroxide in the presence of triethylbenzylammonium chloride (TEBA) gave 3,3,4,4-tetraethoxybut-1-yne (TEB) in excellent yield. This alkyne appears to be thermally stable at least up to 150 °C. The compound is also stable in neutral and basic aqueous solutions. In acidic aqueous media, however, TEB is unstable and was converted to one or several products depending on the reaction conditions. The most useful reaction appears to be deketalization to give 1,1-diethoxybut-3-yn-2-one, which was obtained in quantitative yield under the optimum conditions.     

Synthesis and Trapping of Some Substituted 1-Bromocyclopropenes

Treatment of a number of 2-substituted 1,1,2-tribromocyclopropanes with MeLi at −78°C gave the corresponding 1-bromocyclopropenes, which were reacted with three cyclic dienes to yield the [4 + 2]-cycloadducts. Cycloaddition with 1,3-diphenylisobenzofuran (DPIBF) gave the exo adducts, in most cases in excellent yield, whereas cyclopentadiene afforded endo adducts only, but in moderate yield. In most reactions with furan no adduct was formed, but two 1-bromocyclopropenes derivatives with an aromatic side chain were exceptions and furnished mixtures of exo and endo adducts in moderate yields.     

Synthesis and Trapping of Some Substituted 1-Bromocyclopropenes

Summary. Treatment of a number of 2-substituted 1,1,2-tribromocyclopropanes with MeLi at −78°C gave the corresponding 1-bromocyclopropenes, which were reacted with three cyclic dienes to yield the [4 + 2]-cycloadducts. Cycloaddition with 1,3-diphenylisobenzofuran (DPIBF) gave the exo adducts, in most cases in excellent yield, whereas cyclopentadiene afforded endo adducts only, but in moderate yield. In most reactions with furan no adduct was formed, but two 1-bromocyclopropenes derivatives with an aromatic side chain were exceptions and furnished mixtures of exo and endo adducts in moderate yields.     

THE PRESSURE GRADIENT FORCE IN SIGMA-CO-ORDINATE OCEAN MODELS

The error in computing the horizontal pressure gradient force near steep topography is investigated in a primitive equation, σ-co-ordinate, numerical ocean model (Blumberg and Mellor, in Three -Dimensional Coastal Ocean Models, Vol. 4, American Geophysical Union, Washington D.C., 1987, pp. 1–16). By performing simple test experiments where the density field is allowed to vary in both the vertical and the horizontal direction, severe errors are detected in the areas where the isopycnals hit the sloping bottom. An alternative method of computing the pressure force (Stelling and van Kester), Int. j. numer. methods fluids, 18 , 915–935 (1994) is adopted, resulting in substantial reduction of the errors. However, a systematic underestimation of the calculated quantities is revealed, leading to erroneous depth-mean values of the pressure force. In this study a modification of the Stelling and van Kester method is proposed which seems to improve the overall performance of the method. © 1997 by John Wiley & Sons, Ltd. Int. j. numer. methods fluids 24: 987–1017, 1997.