Hydrogenation without a transition-metal catalyst: on the mechanism of the base-catalyzed hydrogenation of ketones

The hydrogenation of unsaturated organic substrates such as olefins and ketones is usually effected by homogeneous or heterogeneous transition-metal catalysts. On the other hand, a single case of a transition-metal-free and purely base-catalyzed hydrogenation of ketones was reported by Walling and Bollyky some 40 years ago. Unfortunately, the harsh reaction conditions (ca. 200 degrees C, >100 bar H(2), potassium tert-butoxide as base) limit the substrate spectrum of this reaction to robust, nonenolizable ketones such as benzophenone. We herein present a mechanistic study of this process as a basis for future rational improvement. The base-catalyzed hydrogenation of ketones was found to be irreversible, and it shows first-order kinetics with respect to the substrate ketone, hydrogen, and catalytic base. The rate of the reaction depends on the type of alkali ion present (Cs > Rb - K > Na > Li). Using D(2) instead of H(2) revealed a rapid base-catalyzed isotope exchange/equilibration between the gas phase and the solvent as a concomitant reaction. The degree of deuteration of the product alcohols did not indicate a significant kinetic isotope effect. It is proposed that both ketone reduction and isotope exchange proceed via similar six-membered cyclic transition states involving the H(2)(D(2))-molecule, the alkoxide base, and the ketone (solvent alcohol in the case of isotope exchange). Mechanistic analogies are pointed out which apparently exist between the base-catalyzed hydrogenation of ketones studied here and the Ru-catalyzed asymmetric ketone hydrogenation developed by Noyori. In both cases, heterolysis of the hydrogen molecule appears to be assisted by a Br?nsted-base (i.e., alkoxide), the latter being bound to the substrate ketone or the catalyst ligand, respectively, by a bridging Lewis-acidic alkali ion.     

Biogenic substances in sediments and fossils

Most sedimentary rocks contain small concentrations of finely divided organic material. With the aid of modern analytical methods, samples of such rocks can be examined in detail, and conclusions can be drawn concerning the origin of the organic substances. Intact or modified biogenic compounds such as paraffins, isoprenoids, alcohols, ketones, carboxylic acids, steroids, triterpenes, and porphyrins have been isolated from the soluble fractions of the organic material of many sediments and from identified fossils of various geological ages. Even Precambrian rocks contain biogenic substances, so that life forms must have existed more than three billion years ago. The main component of the organic material is “kerogen”, the complicated polymeric structure of which has not yet been established.     

Simultane Ionen-Chromatographie von Kationen und Anionen mit Komplexonen als Elutionsmittel und selektiver UV-Detektion

Summary The complexones EDTA, DCTA and EGTA were investigated as eluting agents at various pH-values for the simultaneous separation of 9 cations and 6 anions using ion chromatography on a silica gel based anion exchanger (Nucleosil 10-Anion II). 1,2-Diaminocyclohexanetetraacetic acid (DCTA) proved to be the best eluting agent. UV spectrophotometry was used for both direct and indirect detection of the anions and anionic metal complexes and a detailed study was carried out with respect to selectivity of detection. This was facilitated by referring to the UV absorption spectra of the anions and metal complexes involved. By choice of a suitable wavelength between 203 and 270 nm and taking into account pH effects, a number of selective determinations were possible. Examples include Pb and Cu in the presence of excess of Ca and Mg as well as nitrate, nitrite and bromide in a large excess of chloride and sulphate. Some examples of detection limits are (g/l) nitrate 2, Fe(III) 3, Cu 9 and Pb 12 (sample volume 20 l, direct UV-detection). The Chromatographie behaviour of Fe(II) and Fe(III) was studied and discussed. Drinking water was analysed for chloride, nitrate and sulphate as well as Ca and Mg using DCTA in the eluent. Complete analyses can be carried out in less than 15 min.

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Herrn Prof. Dr. R. Neeb zum 60. Geburtstag gewidmet     

Bifunctional pincer-type organometallics as substrates for organic transformations and as novel building blocks for polymetallic materials

The reactivity of the bifunctionalized ligand NC(Br)N-I 1 [IC(6)H(2)(CH(2)NMe(2))(2)-3,5-Br-4] has been studied as a versatile synthon for organic and/or organometallic synthesis. Chemoselective metalation (M = Pd, Pt, Li) at the C(aryl)-I or C(aryl)-Br bonds was achieved by choosing the appropriate metal precursors. In this way a series of Pt(II) and Pd(II) complexes were prepared that have a second functional group available for further reactions. These Pt(II) and Pd(II) complexes were subjected to a wide range of organic and organometallic reactions, revealing the remarkable stability of their M-C sigma-bond and opening an easy route for the synthesis of mono- and (hetero)bimetallic building blocks. The scope of the chemistry of such building blocks shows that they are good candidates for use in the synthesis of dendrimers, bioorganometallic systems, or polymetallic materials. The X-ray crystal structures of the most representative complexes (2, 3a, 19, 20, and 24) are also reported.     

Intramolecular easily polarizable charged and non-charged hydrogen bonds: IR continua and hydrogen bond length

Substances with intramolecular, easily polarizable hydrogen bonds of different length are compared. Long hydrogen bonds cause IR continua which show band-like structures in the region 2800–1800 cm^?1, extending with weaker intensity toward smaller wave-numbers over the whole region studied. Medium length bonds cause continua beginning at 3200 cm^?1 and extending over the whole region studied. Very short, easily polarizable hydrogen bonds, such as the bond in the HAuCl₄ salt of NN'-tetramethyl-o-xylildiamine di-N-oxide, cause continua with very great intensity in the region 1500–850 cm^?1. Comparison of the experimental with calculated continua shows very good agreement with regard to wavenumber regions in which easily polarizable hydrogen bonds of different length cause IR continua.By comparing all these intramolecular, easily polarizable hydrogen bonds causing IR continua it is shown that the charge of the hydrogen bonds is not the decisive property for the occurrence of the continua but rather the shape of the proton potentials. Continua may occur only with hydrogen bonds with double minima or broad flat proton potential.     

A Stereoselective Synthesis of (±)-cis-γ-Irone

(±)-cis-γ-Irone( 1 ), a main constitutent of natural iris oil, has been stereoselectively synthesized from methyl (2E)-3 -[(2,2,4-trimethyl-3-cyclohexen-1-yl)methoxy]-2-propenoate (3) (6 steps, overall yield 14%). The cis-configuration as the exocyclic position of the double bond of 1 were secured by the thermal ene reaction of the β-(alkenyloxy)acrylate 3 yielding the 3-oxabicyclo [3,3,1] nonane derivative 5 .     

Comparison between capillary electrophoresis and ion-chromatography for analysis of inorganic anions

Separation and detection of some selected inorganic anions with capillary electrophoresis are shown. The anions are separated in microbore capillaries (25 m* 0.2 m) and detected with a UV-detector. Results are compared with the method of ion exchange chromatography. In consideration of the most important physical and chemical parameters an easy kind of computer simulation for such electropherograms was developed.To get optimal results of separation and UV-detection in capillary electrophoresis some parameters of the device HPE 100, i.e. loading time in the electrokinetic sample injection mode and the running voltage are varied. The behaviour of absorption in the UV region of the chosen anions as well as the influence of pH values in retention behaviour are investigated. There is a simple way to calculate the electrophoretic mobilities from known retention times. Approximate limits of detection for all anions and for each technique are given.     

Beiträge zur Chemie der Pyrrolpigmente, 19. Mitt.: Die elektrochemische Oxidation von Pyrromethenonen und Pyrromethenen (Gallenpigment-Partialstrukturen)

The electrochemical oxidation of arylmethylene-pyrrolinones, pyrromethenones and pyrromethenes as representative bile pigment partial structure models was investigated by means of a rotating disc platinum electrode using acetonitrile as the solvent. Two different oxidation reactions were found. The first reaction being a reversible one-electron oxidation with compounds of the arylmethylene-pyrrolinone series and pyrromethenones which are unsubstituted in position 5 of the pyrrole ring. A two step reaction (the first one reversible, the second irreversible) on the other hand was found to be typical for pyrromethenones bearing a methyl group in this position.Through protonation the first step is at a higher potential, whereas the second one is lowered and becomes reversible. The resulting oxidation pattern can be interpreted analogous to the oxidation of hydroquinones in aprotic solvents.The geometrical isomers of a pyrromethenone were oxidized at appr. the same potential, but there is a strong dependence of the potential of the first oxidation step on the substitution: a higher degree of alkylation favours oxidation by lowering the oxidation potential.

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Mit 1 Abbildung     

Refinement of borate structures from 11B MAS NMR spectroscopy and density functional theory calculations of 11B electric field gradients

The refinement of borate structures using DFT calculations combined with experimental (11)B quadrupole coupling parameters from solid-state NMR spectroscopy is presented. The (11)B electric field gradient (EFG) tensors, calculated using the WIEN2k software for trigonal and tetrahedral boron sites in a series of model compounds, exhibit a convincing linear correlation with the quadrupole coupling tensor elements, determined from (11)B MAS NMR spectra of the central or satellite transitions. The model compounds include Li(2)B(4)O(7), Mg(2)B(2)O(5), Mg(3)B(2)O(6), NH(4)B(C(6)H(5))(4), and colemanite (CaB(3)O(4)(OH)(3).H(2)O). The (11)B quadrupole moment, Q = 0.0409 +/- 0.0002 barn, derived from the linear correlation, is in excellent agreement with the accepted value for Q((11)B). This demonstrates that DFT (WIEN2k) calculations can provide precise (11)B quadrupole coupling parameters on an absolute scale. On the other hand, DFT calculations based on the reported crystal structures for datolite (CaBSiO(4)(OH)) and danburite (CaB(2)Si(2)O(8)) cannot reproduce the experimental (11)B quadrupole coupling parameters to the same high precision. However, optimization of these structures by minimization of the forces between the atoms (obtained by DFT) results in a significant improvement between the calculated and experimental (11)B quadrupole coupling parameters, which indicates that reliable refinements of the borate structures are obtained by this method. Finally, the DFT calculations also provide important structural information about the sign and orientation of the EFG tensor elements in the crystal frame, a kind of information that cannot be achieved from (11)B NMR experiments on powdered samples.