Preparation of stationary phases for open-tubular capillary electrochromatography using the sol-gel method

Capillary electrochromatography requires the deposition of a stationary phase inside the capillary. In this paper the sol-gel method is proposed for this purpose. The gels were prepared externally and injected into a fused-silica capillary, where anchorage to the capillary wall was possible through condensation reactions between the silanol groups of the capillary wall and the residual silanol groups the gel. Contrary to a commonly used practice, alkaline pretreatment of the inner capillary wall prior to the introduction and anchoring of the gel was found to be only marginally effective in improving the mechanical stability of the column. The influence of various parameters, such as the pH, the water content, the presence of alcohol (ethanol) on the formation of tetraethoxysilane (TEOS)-n-octyltriethoxysilane (C8-TEOS) hybrid gels of varied composition is discussed. The pH and the amount of water present were found to be the determining factors in the preparation of a stable gel with the desired mechanical and chromatographic properties. By carrying out the gel formation at 80 degrees C, capillary columns could be produced in 2.5 h. While an acidic pH was required during (external) gel formation, subsequent treatment of the gel inside the capillary with an alkaline solution ('aging') was found to improve separation and stationary phase capacity significantly. The capillary columns were subsequently used to separate a mixture of polycyclic aromatic hydrocarbons in less than 3 min.     

Asymmetric Strecker synthesis by addition of trimethylsilyl cyanide to aldehyde SAMP-hydrazones

The asymmetric 1,2-addition of trimethylsilyl cyanide to aldehyde SAMP-hydrazones in the presence of titanium tetrachloride and diethylether in dichloromethane at −100°C up to room temperature, removal of the chiral auxiliary and acid hydrolysis affords α-amino acids in high enantiomeric excesses (ee=94-97%).     

Palladium-catalyzed, stereoselective rearrangement of a tetracyclic allyl cyclopropane under arylation

The first example of a pi,sigma domino-Heck reaction under concomitant rearrangement of the tetracyclic allylcyclopropane endo,exo-bishomobarrelene (5) is reported; the stereoselective reaction proceeds via an intramolecular insertion of a primarily-formed carbopalladation intermediate into a strained cyclopropane C-C sigma-bond, giving 9.     

Synthese,IR-Spektrum und Kristallstruktur von N,N'-Bis(trimethylsilyl)benzamidinium-tetrachloroferrat(III)

Synthesis, IR Spectrum, and Crystal Structure of N,N'-Bis(trimethylsilyl)benzamidinium Tetrachloroferrate(III) The title compound [C₆H₅? C(NHSiMe₃)₂][FeCl₄] is obtained by the reaction of FeCl₃ with N,N,N'-tris(trimethylsilyl)benzamidine in the presence of tetrahydrofurane, forming yellow, moisture sensitive crystals. The compound is characterized by its IR spectrum as well as by an X-ray structure determination. Space group P2₁/n, Z = 8, 5974 independent observed reflexions, R = 0.066. The lattice dimensions are at ?70°C: a = 2110.7, b = 1109.5, c = 2120.4 pm; β = 111.17º. The compound forms ion pairs, in which the H atoms of the amidinium cation are coordinated with one chlorine ligand of the FeCl₄^? ion in a chelating manner.     

The phenolic oxidation of a β-methylchalcone

The phenolic oxidation of 2',4-dihydroxy-4'-methoxy-β-methylchalcone using alkaline potassium ferricyanide gives an aurone rather than an isoflavone. This result is discussed in the context of current theories regarding the biosynthesis of flavonoid and isoflavonoid compounds.     

Beitrag zur Analyse von Stibin

Zusammenfassung Es wird ein Verfahren zur Bestimmung von Stibin beschrieben, das sich sowohl zur Analyse von SbH₃ in organischen Lösungsmitteln als auch zur Bestimmung von flüssigem oder festem SbH₃ eignet. Hierbei wird das Stibin mit überschüssigem Brom zu Sb^V oxydiert, danach mit SO₂ zu Sb^III reduziert und dieses oxydimetrisch mit Jod oder Bromat titriert.

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Summary A method is proposed for the determination of stibine, applicable to its solutions in organic solvents and also to the solvent-free liquid or solid substance. The procedure involves oxidation of SbH₃ with an excess of bromine to Sb^V, reduction to Sb^III with SO₂, and oxidimetric titration of the trivalent antimony with iodine or bromate.

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Herrn Professor Dr. C. Mahr zum 65. Geburtstag gewidmet.     

Cover Picture

The cover picture shows a model of the "progenitor-TADDOLs" in front of a panorama of the Fünffingersstocks and the Wenden Glacier in the Titlisgebiet (Switzerland). The model is flanked by a stylized view of the general mechanistic model for the preferred stereochemical pathway of the Ti-TADDOLate-catalyzed reaction of chelating substrates (left) and a blackboard (right) showing formulae of compounds that can be prepared with high enantioselectivity by nucleophilic addition in the presence of titanium TADDOLates. From TADDOL, introduced in 1982, a genuine auxiliary system for the "introduction of chirality" (not only by reaction) has been developed, which, in the final sprint against the competition has a good chance of securing a place on the winning podium. The photograph of the mountain landscape was taken by Dr. J. Frackenpohl, the cover picture was generated by one of the authors (A.H.) of the comprehensive review of TADDOLs in this issue (p. 92 ff.) with the help of the program Povray. Supporting information for this article is available on the WWW under http://www.angewandte.com or from the author.     

Efficient synthesis of sulfonic,phosphoric, and phosphinic esters employing alkylating polymer-bound reagents

The efficient esterification of various sulfonic acids and sulfonates using polymer-bound triazenes based on the triazene T2 linker is described. Esterification of enantiopure alpha-substituted sodium sulfonates was performed in the presence of an alkylating resin without racemization. Racemization is a serious drawback in the esterification route via sulfonyl chlorides because of intermediate sulfene formation. To demonstrate the versatility of this protocol, phosphoric and phosphinic acids have been converted into the corresponding esters as well. All products were obtained in good yield and excellent purities without any further purification steps.