Phosphorsäurebis(trimethylsilyl)ester des 1,1,1,4,4,4-Hexafluor-2,3-bis(trifluormethyl)-2,3-butandiols und des 1,1,1,3,3-Pentafluor-2-propenols

Bis(trimethylsilyl)phosphates of 1,1,1,4,4,4-Hexafluoro-2,3-bis(trifluoromethyl)-2,3-butanediol and 1,1,1,3,3-Pentafluoro-2-propenol The monocyclic phosphorane (EtO)₃P[OC(CF₃)₂C(CF₃)₂O] 1 was hydrolized to give a mixture of an acyclic and a cyclic phosphate, 3 and 4 . The trihydroxyphosphorane 2 could not be obtained. Iodotrimethylsilane 6 converts 1 into the silylated derivative of 4 which was found also besides (Me₃SiO)₂P(O)OC(CF₃)₂C(CF₃)₂OSiMe₃ 8 in the reaction of 3 and 4 with Me₃SiCl/(Me₃Si)₂NH. (Me₃SiO)₃P 10 and hexafluoroacetone did not yield the tris(trimethylsiloxy)phosphorane 5 , but the phosphonate 11 which gave (Me₃SiO)₂P(O)OC(CF₃) ? CF₂ 12 upon heating with the loss of fluorotrimethylsilane.     

Synthesis of Tricyclic (λ5)-Phosphoranes; unusual N-demethylation/N-alkylation reactions during the oxidative addition of hexafluoroacetone and tetrachloro-ortho-benzoquinone to benzodiaza-λ3-phosphorinones. Single crystal X-ray diffraction studies of various products

The reaction of methylisatoic acid anhydride 1 with benzylamines led to the N-benzyl-N′-methylanthranilamide derivatives 2 – 4 . Their reaction with phosphorus trichloride furnished the 2-chloro-1-halobenzyl/benzyl-3-methyl-4(1 H)-1,3,2-benzodiazaphosphorin-4-ones 5 – 7 which, upon reaction with bis-(2-chloroethyl)ammonium chloride/triethylamine, were converted into the P-bis-(2-chloroethyl)amino-1-halobenzyl/benzyl-3-methyl-4(1 H)-1,3,2-benzodiazaphosphorin-4-ones 8 – 10 and 12 . With 2-chloroethylammonium chloride/triethyl-amine the P? NHCH₂CH₂Cl-substituted compound 11 was obtained from the P^IIICl-species 6 . The reaction of 8 – 10 and 12 with hexafluoroacetone (HFA) took an unusual course: apart from the oxidative addition of HFA and formation of the perfluoropinacolyl ring system, one of the two CH₂CH₂Cl groups was found to alkylate the CH₃N atom with formation of a five-membered (diazaphospholane) ring in the tricyclic phosphoranes 13 – 16 . The reaction of 11 with HFA also produced a spirophosphorane 17 which involved a λ⁵-oxazaphosphetidine ring system. In the reaction of 8, 10 and 12 with tetrachloro-o-benzoquinone, an oxidative addition reaction with concomitant N-alkylation and formation of the tricyclic phosphoranes 18 – 20 was found to take place. Single crystal X-ray structure determinations are described for the phosphoranes 13, 14 and 16 , and for the precursor compound 9 . The following features are common to the isostructural compounds 13 and 16 and the diethyl ether hemisolvate of 14 : the (λ⁵)-spiro phosphorus atom lies out of the plane of the other atoms of the rings to which it is common, and the dioxaphospholane rings display a twist conformation. In the λ³P-compound 9 the phosphorus atom also lies out of the plane of the other ring atoms.     

Consistency of surface mechanical properties of spread protein layers at the liquid–air interface at different spreading conditions

Π/A isotherms of spread β-lactoglobulin and β-casein at the air–water interface are measured under different spreading conditions. While the isotherms do not show drastic effects of the spreading concentration and the compression rate the interfacial shear rheological behaviour is significantly influenced. In particular, the shear viscosity of β-lactoglobulin layers depend directly on the spreading concentration. Significant viscosity increase is obtained at larger surface pressures when the spreading concentration is increased. In contrast the shear rheology of the spread β-casein layers can be normalised by plotting the viscosities as a function of the surface pressure Π. The different behaviour is discussed in terms of denaturation of the β-lactoglobulin during the monolayer formation process by adsorption from the spread thin protein solution layer.     

Assignment of Relative Configuration to Acyclic Compounds Based on (13)C NMR Shifts. A Density Functional and Molecular Mechanics Study

1,3-Dimethylated hydrocarbon segments occur frequently as structural elements in polyketide natural products. The (13)C NMR chemical shifts of a series of model compounds containing such segments can be well reproduced by a combination of molecular mechanics and SOS-DFPT/IGLO calculations. (13)C NMR chemical shifts are calculated on MM3 geometries and are Boltzmann weighted according to the MM3 energies. On the basis of the resulting thermally averaged chemical shifts, all diastereomers of the model compounds can be unequivocally distinguished. Significant differences in chemical shifts occur at methyl groups and methylene groups that are adjacent to a single stereogenic center. The method is applied to predict the relative configuration of two stereocenters in the side chains of two natural products, sambutoxin and the bradykinin inhibitor L-755,897.     

Polyhedral clathrate hydrates of a strong base: Phase relations and crystal structures in the system tetramethylammonium hydroxide-water

The tetramethylammonium hydroxide-water system has been studied by low-temperature differential thermal analysis and X-ray powder diffraction. The melting diagram was constructed for concentrations between 66.7 and 100 mol% H₂O. It shows the existence and stability ranges of as many as eight crystalline hydrate phases:- and-Me₄NOH·2H₂O (phase transition at –85°C, decomposition atca. 105°C), Me₄NOH·4 H₂O (melting point 44°C, incongruent), and-Me₄NOH·5 H₂O (phase transition at 42°C, melting point 68°C, congruent),- and-Me₄NOH·7.5 H₂O (phase transition at 6°C, melting point 16°C, incongruent), and Me₄NOH·10 H₂O (melting point –20°C, incongruent). The structures of all these phases, except the already known one of-Me₄NOH·5 H₂O, were determined from single-crystal MoK diffractometer data. The decahydrate and the high-temperature forms of the 7.5-hydrate and the pentahydrate are genuinepolyhedral clathrate hydrates, the first ones reported of a strong base. Their mostly novel three-dimensional anionic host structures, formed by the hydrogen-bonded OH^– ions and H₂O molecules, arefour-connected throughout, in spite of their proton deficiency which is apparently leveled by disorder. Disorder also affects the enclosed cationic Me₄N⁺ guest species. Like the low-temperature form of the pentahydrate, that of the 7.5-hydrate has a clathrate-related, but not fully polyhedral structure, some of the oxygen atoms being three-connected only. The tetrahydrate presents the rare case of both a hydrogen bond of the type OH^–...OH₂ and a (deprotonated) water-channel structure. This is fully ordered and apart from that can be derived from the polyhedral one of the-pentahydrate just by removing the appropriate number of water molecules from certain positions. The structures of- and-Me₄NOH·2 H₂O contain identical one-dimensionalspiro chains [HO^–(HOH)_/42] with the hydroxide protonnot participating in the hydrogen bonding. The Me₄N⁺ ion is ordered in the and disordered in the phase.Supplementary Data relating to this article are deposited with the British Library as Supplementary Publication No. SUP 82076 (66 pages).Dedicated to Dr D. W. Davidson in honor of his great contributions to the sciences of inclusion phenomena.     

An Unexpectedly Stable Chiral Hydrido-Solvent Complex of RuII: A mechanistic link in the enantioselective hydrogenation of pyrones. Preliminary communication

The ligand (6,6′-dimethoxybiphenyl-2,2′-diyl)bis[3,5-di(tert-butyl)phenylphosphine] ( 1 ) forms an unexpectedly stable hydrido-bis-solvento complex of composition [RuH(isopropanol)₂( 1 )]BF₄, ( 2 ) under the conditions used in the enantioselective hydrogenation of pyrones. The structure of 2 , determined by X-ray diffraction, represents the first well-characterized chiral five-coordinate bis-phosphine ruthenium-hydride complex stable as a solvento complex, and provides a structural link in the enantioselective pyrone hydrogenation cycle catalyzed by [Ru(OAc)₂( 1 )]. Using the arene complex [RuH(p-cymene)( 1 )]BF₄ ( 3 ), the chiral pocket of coordinated 1 is shown to be relatively rigid, via NMR spectroscopy. This is reflected in restricted rotation about one of the four P–[3,5-di(tert-butyl)phenyl] P? C_ipso bonds at room temperature.     

Staudinger – Reaktionen am Bornanylen(dimethylphosphino)methylimin. Phosphorylierung des dabei gebildeten Trimethylsilylphosphinimids mit Diorganochlorphosphinen: unerwartete Bildung von Verbindungen mit P=N–P–P-Einheiten

Staudinger Reactions with Bornanylene(dimethylphosphino)methylimine. Phosphorylation of the Trimethylsilylphosphine Imide formed with Diorganochlorophosphines: unexpected Formation of Compounds with P=N–P–P Units Phosphinimido derivatives of the chiral bornanylene(dimethylphosphino)methyl imine have been obtained from its reactions with trimethylsilyl-, phenyl- and 4-nitrobenzoyl azide. A single crystal X-ray structure determination has been conducted on the 4-nitro-benzoylphosphinimido derivative of bornanylene(dimethylphosphino)methyl imine. The compound was found to crystallize with two independent molecules in the chiral monoclinic space group P2₁. The trimethylsilylphosphinimido derivative of bornanylene(dimethylphosphino)methyl imine was allowed to react with diorgano-chlorophosphines, with unexpected formation of compounds with PP-bonded RR′₂P=N–P⁽⁺⁾R″₂–PR″₂ groups. The ³¹P-NMR spectra of two representative compounds are simulated and discussed.     

MaxSynBio: Avenues Towards Creating Cells from the Bottom Up

A large German research consortium mainly within the Max Planck Society (“MaxSynBio”) was formed to investigate living systems from a fundamental perspective. The research program of MaxSynBio relies solely on the bottom‐up approach to synthetic biology. MaxSynBio focuses on the detailed analysis and understanding of essential processes of life through modular reconstitution in minimal synthetic systems. The ultimate goal is to construct a basic living unit entirely from non‐living components. The fundamental insights gained from the activities in MaxSynBio could eventually be utilized for establishing a new generation of biotechnological processes, which would be based on synthetic cell constructs that replace the natural cells currently used in conventional biotechnology.