Regioselective photoallylations of dicyanopolycyclic aromatic compounds via electron transfer

Upon irradiation with allyltrimethylsilane, dicyanopolycyclic aromatic compounds undergo two modes of photoallylations, depending on the compounds and the reaction conditions. Both the photoreactions occur in a highly regioselective manner via electron transfer.     

Low-temperature viscoelasticity of poly-oxymethylene by radiation-induced solid-state polymerization of trioxane single crystal

Summary The polymerizate is a porous, white cylinder of polyoxymethylene, whose direction of crystal axis is unique. The dynamic viscoelasticity was measured by the vibrating-reed-method at –180° +10 °C. The existence of the -dispersion is doubtful in this sample. Therefore we can conclude that (i) the amorphous part is negligibly small both on the surface and inside of this sample, and (ii) the vibration of molecular chains is prohibited even on the surface of a single crystal.

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Zusammenfassung Das Polymerisat ist ein poröser, weißer Zylinder von Polyoxymethylen mit einheitlich ausgerichteter Kristallachse. Die dynamische Viscoelastizität wurde zwischen –180° und +10 °C nach der Methode des vibrierenden Stäbchens bestimmt. Die Existenz des-Dispersionsgebiets ist bei dieser Probe zweifelhaft. Wir können daher folgern, daß 1. der amorphe Anteil vernachlässigbar klein — sowohl an der Oberfläche wie im Innern — ist und daß 2. die Schwingung der Molekülketten sogar auch in der Grenzfläche eines Einkristalls behindert, unterbunden ist.

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This work was presented at the 43rd Annual Meeting of Virginia Academy of Science, Richmond, Virginia, May 7, 1965.     

Determination of the 17O NMR tensors in potassium hydrogen dibenzoate: a salt containing a short O...H...O hydrogen bond

Solid-state 17O NMR spectra were obtained at 4.70, 11.75 and 19.60T for potassium hydrogen [17O(4)]dibenzoate (PHB) under both magic-angle spinning and stationary conditions. Spectral analyses yielded both the magnitude and orientation of the 17O chemical shift (CS) tensor and the electric field gradient (EFG) tensor for each of the two chemically distinct oxygen sites in PHB. For the oxygen site that is not involved in hydrogen bonding, the experimental 17O NMR tensors are: delta(iso)=287+/-2 ppm, delta(11)=470+/-5 ppm, delta(22)=380+/-5 ppm, delta(33)=10+/-5 ppm, C(Q)=8.30+/-0.02 MHz, eta(Q)=0.23+/-0.05, alpha=0+/-5 degrees, beta=90+/-5 degrees, and gamma=30+/-5 degrees. For the oxygen site in the short O...H...O hydrogen bond, the experimental 17O NMR tensors are: delta(iso)=213+/-2 ppm, delta(11)=370+/-5 ppm, delta(22)=190+/-5 ppm, delta(33)=80+/-5 ppm, C(Q)=5.90+/-0.02 MHz, eta(Q)=0.55+/-0.05, alpha=5+/-5 degrees, beta=90+/-5 degrees, and gamma=90+/-5 degrees. Extensive quantum mechanical calculations at both restricted Hartree-Fock and density functional theory levels were performed to investigate the effects of an effectively symmetrical O...H...O hydrogen bond on 17O CS and EFG tensors.     

Solid-supported Robinson annulation under microwave irradiation

Robinson annulation on alumina occurred efficiently on heating with microwave irradiation.     

Regioselective reductive coupling of alkynes and aldehydes leading to allylic alcohols

Treatment of a mixture of a terminal alkyne and an aldehyde with CrCl(2) and a catalytic amount of NiCl(2) and triphenylphosphine in the presence of water in DMF at 25 degrees C gives a 1,2-disubstituted allylic alcohol regioselectively.     

ENDOR study on the anion radical of benzo[c]cinnoline

The ENDOR spectrum was obtained for the benzo[c]cinnoline anion radicalin 1,2-dimethoxyethane. The hfs constants of the protons correspond with those found by EPR spectroscopy, and also agree well with the qualitative tendency of the reported spin density distributions by HMO calculation.     

Synthesis of (2s, 3r, 7rs)-stegobinone [2,3-dihydro-2,3,5-trimethyl-6-(1-methyl-2- oxobutyl)-4h-pyran-4-one] and its (2r, 3s, 7rs)-isomer : The pheromone of the drugstore beetle

Reaction of acetaldehyde with the trianion of 4,6-dimethylnonane-3,5,7-trione followed by acidification yielded a stereoisomeric mixture of stegobinone, the pheromone of Stegobium paniceum L. Acylation of the dianion derived from 4-methylheptane-3,5-dione with a mixed anhydride prepared from (2R, 3S)-3-hydroxy-2-methylbutanoic acid or its enantiomer led to (2S,3R,7RS)- or (2R, 3S, 7RS)-stegobinone. The natural pheromone possesses (2S,3R)-stereochemistry.