Total synthesis of himandravine

[reaction: see text] The first total synthesis of (+)-himandravine (1) is described, starting from (2S,6S)-cis-2-formyl-6-methyl-N-Boc-piperidine (8) in 11 linear steps and 17% overall yield. The key step involves a highly diastereoselective intramolecular Diels-Alder reaction of the key intermediate 5 that contains the entire latent carbon framework and functional group substitution of himandravine.     

Transmembrane ion conductance by an acyclic bolaamphiphile

[reaction in text] An acyclic bolaamphiphile forms ion channels in vesicles and planar bilayer membranes that are closely similar to the channels formed by related bismacrocyclic compounds. Thus the function of these ion channels does not depend on synthetically difficult macrocyclic subunits.     

The Effects of Beating,Web Forming and Sizing on the Surface Energy of <Emphasis Type="Italic">Eucalyptus globulus</Emphasis> Kraft Fibres Evaluated by Inverse Gas Chromatography

In this work attention has been focused on the effects of papermaking beating, web forming and sizing operations on the physical/chemical surface properties of bleached Eucalyptus globulus kraft fibres. Inverse gas chromatography (IGC) was used to determine the dispersive component of surface tension (γ_s^d) as well as the acidic/basic character (according to the Lewis concept) of the solid surfaces (pulp fibres and pulp handsheets). The results have shown that the main effect of beating is to increase the fibre's Lewis acidic character. Web forming caused a strong decrease in γ_s^d and significant increments in the adhesion works of both acidic and basic probes, lowering the ratio between the two. Nevertheless, the surface of handsheets still exhibited a dominant acidic character. The sizing operation did not change the dispersive component of the surface tension significantly but decreased the difference between the adhesion works of the acidic and basic probes, rendering the handsheet surface less Lewis acidic and more Lewis basic. Thus, although internal sizing is expected to strongly influence liquid spreading at the paper surface and liquid penetration of the fibre's network, it is concluded that beating and web forming lead to important changes in the surface energetic properties of the Eucalyptus globulus kraft fibres.     

Kottamide E, the first example of a natural product bearing the amino acid 4-amino-1,2-dithiolane-4-carboxylic acid (Adt)

Kottamide E, a novel alkaloid containing dibrominated indole enamide, oxalic acid diamide and 4-amino-1,2-dithiolane-4-carboxamide moieties, has been isolated from the New Zealand ascidian Pycnoclavella kottae. Characterisation was achieved by interpretation of spectroscopic data.     

Chromatographic studies of corrosion sites in metallic materials

Many types of corrosion phenomena are controlled by the ionic composition of a small volume of solution at the surface. Localized corrosion and atmospheric corrosion are two examples in which < 1 μl of solution can cause dramatic damage. Ion chromatographic (IC) techniques have been used to analyze these solutions in order to gain a better understanding of the mechanisms which govern them. Two examples are presented. The presence of minor alloying elements at localized corrosion sites in two aluminum alloys has been demonstrated, indicating non-stoichiometric dissolution of the alloy during localized corrosion. In addition, IC analysis allowed the determination of the species responsible for the atmospheric corrosion failure of electrical connectors, including their likely origin.     

High-performance size-exclusion chromatographic determination of the potency of biosynthetic human growth hormone products

A new high-performance size-exclusion chromatography method has been developed for the determination of potency of human growth hormone products. This method has been extensively validated and shown to correlate well with the hypophysectomized rat bioassay which has been used traditionally. The method is much more precise than the traditional bioassay and thus provides more reliable means of producing consistent biosynthetic human growth hormone batches.     

Studies on poly(iminomethylenes)

A variety of simple alkyl and aryl isocyanides have been polymerized using 0.5% NiCl₂ in ethanol as a catalyst. The resulting poly(iminomethylenes) have been characterized by carbon-13 NMR spectroscopy and their polystyrene-equivalent molecular weights have been determined by gel permeation chromatography. Straight chain aliphatic isocyanides having from three to ten carbon atoms in the chain form readily solyble polymers having molecular weights (M_w) in the general range 10,000 to 30,000. Neopentyl isocyanide unlike tert-butyl isocyanide forms an insoluble polymer. A number of new soluble aryl isocyanide polymers have been obtained. However, aryl isocyanides having a single alkyl substituent (CH₃, C₂H₅, CF₃) in the ortho position give only insoluble polymers, whereas aryl isocyanides having alkyl substituents in both ortho positions (e.g., 2,6-(CH₃)₂C₆H₃NC and 2,4,6-(CH₃)₃C₆H₂NC) fail to polymerize under these conditions. The highest molecular weight soluble aryl isocyanide homopolymer is obtained from 3-CH₃OC₆H₄NC(M_w = 26,000). The trimethylsilyl substituted isocyanide (CH₃)₃SiCH₂CH₂NC has been obtained from LiCH₂NC and (CH₃)SiCH₂Cl and gives a brown soluble homopolymer with a molecular weight (M_w) of 19,000.     

Substituted chromans and tetrahydrofuro[2,3-b]benzofurans (trapped tetrahedral intermediates) from 3-phenyl-2-benzofuranones

The previously discovered neighboring group reaction has been extended to the synthesis of chroman derivatives (i.e., 4, 5, 6) containing geminal methyls in the 2-position, a feature common to certain physiologically active natural chromans. In two instances, cyclic ortho ester by-products (8), not observed in previous work, were formed as a result of the intramolecular trapping of tetrahedral intermediates. Reasons for the incursion of this unexpected side reaction are discussed.     

Photoelectron spectra of polyunsaturated [4,4,2]propellanes

The photoelectron spectra of the six propellanes 1 to 6 have been recorded. Those bands which correspond to ejection of an electron from a π-orbital have been assigned, using the concept of through bond and through space interaction. Homoconjugative interaction between the π-systems of the two butadiene moieties of 6 is of the same order as that of the π-orbitals in norbornadiene.     

Cl35 NQR spectra and the transmission effects in the series RSO2Cl

Conclusions It was shown by correlating the Cl³⁵ NQR frequencies with the Taft _I and _c parameters that the effect of substituents, which are either capable of conjugation (Hal, OR, NR₂) or are alkyl groups, is transmitted to the chlorine atom through the SO₂Cl group by a practically purely inductive means.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 2, pp. 486–488, February, 1970.