Synthesis and characterization of some novel cyanonitrosyl complexes of chromium(I) with Mannich bases,aromatic aldehyde oximes and syn-phenyl-2-pyridylketoxime

Some new low-spin hexacoordinated cyanonitrosyl complexes of Cr¹ of the type [Cr(NO)(CN)₂(L)₂(H₂)], where L is an aromatic aldehyde oxime or Mannich base, have been prepared by the interaction or K₃[Cr(NO)(CN)₅]· H₂O with L in aqueous AcOH, and characterized by a range of physico-chemical techniques, I.r. data suggest that all the oxime derivatives and Mannich bases act as monodentate ligands by coordinating through the aromatic nitrogen. TMC 2564     

Remarkable O(2)-effect in 1,4-additions of diethylzinc to 6-acyloxy-2H-pyran-3(6H)-ones and 6-alkoxy-2H-pyran-3(6H)-ones

Under the influence of air, a facile 1,4-addition of diethylzinc to acyloxypyranones and alkoxypyranones 1 takes place. Reaction of diethylzinc with molecular oxygen provides EtOOZnEt, which catalyzes the addition of diethylzinc.     

Syntheses of Some 3—[1′（1′H）—Substituent—pyrazol—5′—yl] benzo [5,6] coumarins

3-[1′(1′H)-Substituent-pyrazol-5′-yl]benzo[5,6]coumarins and 3-(1′,2′-oxazol-5′-yl)benzo[5,6]coumarin were prepared via condensation of 3-(2′-formyl-1′-chlorovinyl)benzo[5,6] coumarin with hydrazine derivatives or hydroxylamine.Reaction of 3-[1′(1′H)-pyrazol-5′-yl]benzo[5,6]coumarin with alkyl halides,olefinic compunds or acid chlorides are described.     

Effects of concentration on the partitioning of macromolecule mixtures in agarose gels

To test the effects of solute concentration on the equilibrium partitioning of single macromolecules and macromolecule mixtures between bulk solutions and gels, the partition coefficient in agarose was measured for BSA and for four narrow fractions of Ficoll with Stokes radii of 30-59 A. Solutions of each test macromolecule were equilibrated with a known volume of gel, final liquid concentrations measured, and partition coefficients (gel concentration divided by bulk concentration) calculated by applying a material balance. The partition coefficient of each macromolecule was measured in 4 and 6% gels under dilute conditions and with BSA present at initial concentrations up to 13.5 g/dl. As expected, the partition coefficients decreased with increasing agarose concentration and with increasing macromolecular size. Moreover, increasing the BSA concentration increased the partition coefficient of BSA itself and that of all four Ficolls. This effect was most pronounced for the largest test solutes. Measurements at two ionic strengths confirmed that electrostatic interactions were negligible under the conditions used. The experimental results were compared with predictions from a previously developed excluded volume theory for the partitioning of mixtures of rigid, spheroidal macromolecules in fibrous media. Agarose was represented as a randomly oriented array of cylindrical fibers, BSA as a prolate spheroid, and Ficoll as a sphere. The quantitative agreement between the model predictions and the data was generally quite good, indicating that steric interactions among solute molecules and between solute molecules and gel fibers could explain the partitioning results. The theory is simple enough computationally to be applied to a variety of processes that are influenced by the equilibrium partitioning of macromolecules.     

The ready conversion of anguidine into verrucarol and trichodermol

Anguidine, $\text{1}$, is readily converted into verrucarol diacetate, $\text{2d}$, in 85 percent yield by application of the Barton-McCombie deoxygenation procedure. To enable conversion into trichodermol, $\text{3a}$, the primary hydroxyl group of verrucarol, $\text{2a}$, is selectively acetylated or is selectively acetylated or preferably silylated, thereby paving the way for its deoxygenation in three simple, high-yield reactions.     

Influence of liquid layers on energy absorption during particle impact

The influence of the thickness of a covering liquid layer and its viscosity as well as the impact velocity on energy loss during the normal impact on a flat steel wall of spherical granules with a liquid layer was studied. Free-fall experiments were performed to obtain the restitution coefficient of elastic–plastic Al2O3 granules by impact on the liquid layer, using aqueous solutions of hydroxypropyl methylcellulose with different concentrations for variation of viscosity (1–300 mPa s). In the presence of a...     

The diffraction of elastic waves by an imperfect fusion bond

We consider diffraction by a semi-infinite crack located alonga fusion interface between two differing elastic media. Twotypes of crack, namely open and partially closed cracks, areinvestigated. An open crack is modelled by a stress-free contactboundary condition and a partially closed crack is modelledby a spring contact boundary condition. For the latter, thejump in the stress across the crack is assumed to be proportionalto the jump in the displacement across the crack. This situationarises in, for example, a K-weld where the fine grain of theparent material (for example, ferritic or forged austeniticsteel) is in stark contrast with the coarse-grained weld metal(for example, austenitic weld metal). In the metal weld thedirection of the grain axis varies through the metal. However,diffraction is a local phenomenon and so the austenitic steelis assumed to have a zonal axis so that it may be modelled bya transversely isotropic composite. The ferritic or forged austeniticsteel will be modelled as an isotropic material.     

Studies directed at the synthesis of verrucarol from D-glucose: the A-B moiety

The Claisen rearrangement of an ally vinyl ether residue elaborated at C4 of a pyranoside ring, occurs with β-stereoselectivity leading predominantly to the isomer having the ethylene and acetaldehyde groups in equatorial and axial orientations respectively. The acetaldehyde moiety is extended to a butanoate, and the C5 hydroxymethyl of the sugar is oxidized to an aldehyde. Anionic ring closure of the activated methylene to the aldehyde is induced with sodium hydride, and dehydration to the α,β-unsaturated ester is effected with acetic anhydride in pyridine.