Trifluoromethoxy substituted anilines: metalation as the key step for structural elaboration

Trifluoromethoxy-substituted anilines undergo hydrogen/lithium permutation ("metalation") with optional site selectivity depending on the N-protective group employed. N-tert-Butoxycarbonyl-2- and -4-(trifluoromethoxy)aniline react with tert-butyllithium at the nitrogen-adjacent 6- and 2-position affording, after electrophilic trapping, products 1-6. In contrast, deprotonation of the para isomer occurs at the oxygen-neighboring 3-position, giving rise to the acid 12, when the amino group is carrying two trimethylsilyl groups. sec-Butyllithium attacks 3-trifluoromethoxy-N-mono(trimethylsilyl)aniline at the 2-position, but 3-trifluoromethoxy-N,N-bis(trimethylsilyl)aniline at the 4-position to provide respectively the acids 10 and 11 after carboxylation. The synthesis of two new benzodiazepines illustrates (19 and 22) the preparative potential of the aniline functionalization mediated by organometallic reagents.     

Synthese und Kristallstruktur von Hydronium-tris-ethylendiamin-cobalt(rhodium)-μ-trichloro-nonachlorotrirhenat(II)-chlorid,H3O[MEn3][Re3Cl12]Cl (M=Co,Rh)

Synthesis and Crystal Structure of Hydronium-tris-ethylenediamine-cobalt(rhodium)-μ-trichloro-nonachlorotrirhenate(III)-chloride, H₃O[MEn₃][Re₃Cl₁₂]Cl (M=Co, Rh) The chlorides H₃O[MEn₃][Re₃Cl₁₂]CI (M = Co, 1 ; Rh, 2 ) crystallize from hydrochloric acid solutions of ReCl₃ and MEn₃ · 3H₂O as deep red hexagonal columns. They are isotypic and crystallize with the hexagonal system (P6 , Z = 1; 1: a = 1010.87(3); c = 794.30(4) pm, R = 0.023, R_w = 0.016; 2: a = 1018.58(3); c = 794.74(4) pm, R = 0.026, R_w = 0.018). The anions [Re₃Cl₁₂]^3? are connected via H₃O₊ cation (C.N. 3). The large channels that run in the [001] direction contain, alternatively, the cations [MEn₃]³⁺ and the lonesome Cl^?-anions     

Synthesis and structure of a stabilized 10-membered cyclic enediyne

The synthesis and structure of an acetal protected 10-membered cyclic enediyne-1,2-diol rac-10 is reported. The conformational constrain of the unsaturated macrocycle by the acetal protection group prevents the thermal cyclization reaction of the endiyne during synthesis and purification.     

Enzyme promiscuity: first protein-catalyzed Morita-Baylis-Hillman reaction

The Morita-Baylis-Hillman reaction of cyclohexenone and p-nitro benzaldehyde is catalyzed by carrier proteins such as serum albumins or enzymes such as certain lipases, conversion of up to 35% and enantioselectivities of up to 19% being observed.     

Characterization of individual atmospheric particles by element mapping in electron probe microanalysis

In this paper procedures for the characterization of individual aerosol particles by element mapping in the electron microprobe are presented. The number, size and qualitative chemical composition of particles is derived from a combination of secondary or backscattered electron images and element distribution maps. Accuracy of the size distribution and reliability of the qualitative analysis procedure were checked with silicate samples. In order to obtain a semi-quantitative estimate of the chemical composition of individual particles the count rates taken from element distribution maps are corrected for matrix and geometric effects using particle ZAF procedures.Dedicated to Professor Dr. rer. nat. Dr. h.c. Hubertus Nickel on the occasion of his 65th birthday     

Atom-probe field ion microscopy

The atom probe field ion microscope (AP-FIM) is a combination of a field ion microscope and a time-of-flight mass spectrometer with a single ion detection sensivity. With the field ion microscope topology of a surface, surface reactions and surface modifications can be studied in atomic detail. By time-of-flight measurements surface layers and interface layers can be chemically analyzed atom by atom and atomic layer by atomic layer. Compositional variations according to surface or interface segregation, precipitations, or surface changes in corrosion or in electrochemical layer formation etc. can be studied quantitatively on a subnanometer scale. Some of our studies on related problems will be decribed briefly.     

Photochemical structuring and fixing of structures in binary polymer brush layers via 2pi+2pi photodimerization

Binary polymer brushes grafted to Si wafers were prepared from hydrophilic and hydrophobic polymer components, which allow switching the surface properties (as revealed by contact angles) by exposure to varying solvents. The hydrophilic component was poly-2-vinylpyridine; the hydrophobic component was a copolymer of styrene and 2-(4-vinylphenyl)indene containing the photodimerizable phenylindene chromophore. The brushes were prepared via thermal and via photochemical grafting-to methods, which led to distinct layer thicknesses. Structural patterns differing in surface properties were produced and fixed via crosslinking the hydrophobic component by 2pi+2pi photodimerization of phenylindene moieties. The patterns were visually observable.