Synthesis of 4-acetylisocoumarin: first total syntheses of AGI-7 and sescandelin

A practical synthetic route to 4-acetylisocoumarins and the first total synthesis of AGI-7 (5) and sescandelin (4) are described. The readily available homophthalate 8 was transformed to the vinylogous amide ester 13 in high overall yield. Upon treatment of 13 with refluxing aqueous formic acid, the desired 4-acetylisocoumarin (5) and its regioisomer 3-methyl-4-formylisocoumarin (17) were produced in a 3:1 ratio. After separation of the desired product (5) from the unwanted minor isomer, the enantioselective reduction of AGI-7 by borane in the presence of Corey's (S)-oxazaborolidine reagent afforded (+)-sescandelin (4) with a 93% ee.     

Isolation of essential oils from tobacco by gas co-distillation/solvent extraction

Summary The essential oils have been isolated from tobacco leaves using a simple gas co-distillation apparatus. The method involves co-distillation with water under the continuous stream of an inert gas with subsequent single solvent extraction of the distillate. The extract is analysed on GC and GC/MS in splitless injection mode without further concentration. The method was evaluated for reproducibility using n-octadecane as an internal standard. The distillation-extraction procedure was reporducible with an average deviation of ±3% for the major constituents. The present method was applied to the analyses of the essential oils of other agricultural products.Dedicated to Dr. L. S. Ettre on the occasion of his 60th birthday.     

Vacuum balance and related studies of green and red rusts

Green and red rusts are formed when iron is partially or completely oxidised. Analogues of the rusts may be precipitated from iron(II) and iron (III) salt solutions treated with alkali under reducing or oxidising conditions. Variations in surface area and porosity have been investigated by gravimetric nitrogen gas sorption, using vacuum microbalance techniques.Freshly-precipitated red rusts, hydrous iron (III) oxide, have surface areas of about 200–400 m²g^?1. When they are added to iron (II) hydroxide suspensions kept at pH 7, the green Fe (II)-Fe (III) rusts formed have lower surface areas of about 40–100 m²g^?1, depending on the initial iron(II) sulphate concentrations.     

Nitrato- and fluoroboracites M3B7O13NO3 and M3B7O13F

New boracites containing nitrato- or fluoroanions that appear to be true low-pressure phases have been synthesized at superatmospheric pressures. The M₃B₇O₁₃NO₃ compounds (M = Co, Ni, Cu, Zn, Cd) transform rapidly and reversibly in the temperature region 300–500°C between probable orthorhombic and face centered cubic symmetry, while the M₃B₇O₁₃F compounds (M = Mg, Mn, Fe, Co, Zn) appear to maintain rhombohedral symmetry up to their decomposition temperatures of 800–900°C. True high-pressure boracite-like phases containing F and Cr, Mn, Fe, or Co that decompose upon heating to M₃B₇O₁₃F have also been isolated.     

A Ca2+-phospholipid-dependent protein kinase from cottonplant shoots

The Ca²⁺-phospholipid-dependent protein kinase from cottonplant shoots was purified by chromatography on DEAE-Sepharose CL-6B, and then on phenyl-Sepharose CL-4B. According to electrophoresis in PAAG, the enzyme was practically homogeneous and had a molecular mass of 57 kDa. In the presence of Ca²⁺ alone, the enzyme was activated to only a slight degree. Under the combined action of Ca²⁺ and a phospholipid the action of the enzyme rose severalfold. A determination of amino acid specificity showed that the protein kinase isolated was a serine- and threonine-specific protein kinase.A. S. Sadykov Institute of Bioorganic Chemistry, Academy of Sciences of the Republic of Uzbekistan, Tashkent, fax 627071. Translated from Khimiya Prirodnykh Soedinenii, No. 1, pp. 100–105, January–February, 1994.     

Site-directed exchange studies with combinatorial libraries of nanostructures

We describe a new combinatorial method for studying the exchange between solution adsorbates and nanoscale features within libraries generated via dip-pen nanolithography. Four different compounds, 1-octadecanethiol, 16-mercaptohexadecanoic acid, ferrocene (11-mercaptoundecyl), and ferrocene (11-mercapto-1-oxoundecyl), are studied on amorphous and single-crystal gold substrates. This series of adsorbates allows us to compare the exchange properties of patterns of nanoscale features as a function of composition, feature size, and type of underlying substrate. Moreover, these properties can be compared and contrasted with bulk SAM properties. The novel strategy provides not only a method for initiating site-specific exchange processes but also a way of extracting kinetic information about the rate of such processes in situ.     

Phytochemicals from Echinacea and Hypericum: A Direct Synthesis of Isoligularone

Reaction of trienes with α,β-unsaturated aldehydes produces bicyclic products via a tandem Diels-Alder/ene reaction. The adduct from tiglic aldehyde was converted into isoligularone by conversion to a furan followed by benzylic oxidation.