Water-Soluble Phosphines. 6.(1) Tailor-Made Syntheses of Chiral Secondary and Tertiary Phosphines with Sulfonated Aromatic Substituents: Structural and Quantum Chemical Studies

Chiral water-soluble secondary phosphines (2-6) were obtained by nucleophilic phosphination of FC(6)H(4)-4-SO(3)K (1a), FC(6)H(3)-2,4-(SO(3)K)(2) (1b), and FC(6)H(4)-2-SO(3)K (1c) with RPH(2) (R = Ph, 2,4,6-Me(3)C(6)H(2), 2,4,6-iPr(3)C(6)H(2)) in the superbasic medium DMSO/KOH by employing steric control of substitution at phosphorus by bulky substituents R and sulfonic groups in the ortho position of the aromatic ring systems in 1b or 1c. The secondary phosphines may be deprotonated in DMSO/KOH to give phosphido anions which on reaction with alkyl halides (PhCH(2)Cl, Br(CH(2))(3)Br, and C(12)H(25)Br) yield mono- or bidentate tertiary phosphines (7-10). Ligands of this type are alternatively accessible by nucleophilic arylation of secondary phosphines, e.g. Ph(Me)PH or Ph(H)P(CH(2))(3)P(H)Ph with 1a or 1b, respectively. The crystal structure of the starting material 1b.H(2)O (space group P2(1)/m) has been determined. In the solid state of 1b.H(2)O the individual molecules are interconnected by ionic interactions between the potassium cations and the SO(3)(-) anions. The C-F bond (C(1)-F 1.347(4) ?) is shorter than that in C(6)H(5)F (1.356(4) ?). The unit cell of 7a.0.5H(2)O (space group P&onemacr;), the first structurally characterized chiral phosphine with a sulfonated phenyl substituent, contains the two enantiomers. Due to the asymmetrical substitution at phosphorus the PC(3) skeletons are significantly distorted (P(1)-C(1,11,31) 1.864(10), 1.825(8), 1.841(7) ?). The electronic structure of sulfonated fluorobenzenes FC(6)H(5)(-)(n)()(SO(3)M)(n)() (M = K, NH(4), n = 1-3) is discussed on the basis of quantum chemical calculations. In particular, the reactivity difference toward nucleophilic phosphination within the series is rationalized in terms of steric factors and of the -I effect of the sulfonic groups.     

Modeling the chemistry of plasma polymerization using mass spectrometry

The goal of the project is a solvent free painting shop. The environmental technologies laboratory is developing processes of plasma etching and polymerization. Polymerized thin films are first-order corrosion protection and primer for painting. Using pure acetylene we get very nice thin films which were not bonded very well. By using air as bulk gas it is possible to polymerize, in an acetylene plasma, well bonded thin films which are stable first-order corrosion protections and good primers. UV/Vis spectroscopy shows nitrogen oxide radicals in the emission spectra of pure nitrogen and air. But nitrogen oxide is fully suppressed in the presence of acetylene. IR spectroscopy shows only C=O, CH(2) and CH(3) groups but no nitrogen species. With the aid of UV/Vis spectra and the chemistry of ozone formation it is possible to define reactive traps and steps, molecule depletion and processes of proton scavenging and proton loss. Using a numerical model it is possible to evaluate these processes and to calculate theoretical mass spectra. Adjustment of theoretical mass spectra to real measurements leads to specific channels of polymerization which are driven by radicals especially the acetyl radical. The estimated theoretical mass spectra show the specific channels of these chemical processes. It is possible to quantify these channels. This quantification represents the mass flow through this chemical system. With respect to these chemical processes it is possible to have an idea of pollutant production processes.     

Geometric H/D isotope effects and cooperativity of the hydrogen bonds in porphycene.

We investigate the primary, secondary, and vicinal hydrogen/deuterium (H/D) isotope effects on the geometry of the two intramolecular hydrogen bonds in porphycene. Multidimensional potential energy surfaces describing the anharmonic motion in the vicinity of the trans isomer are calculated for the different symmetric (HH/DD) and asymmetric (HD) isotopomers. From the solution of the nuclear Schr?dinger equation the ground-state wavefunction is obtained, which is further used to determine the quantum corrections to the classical equilibrium geometries of the hydrogen bonds and thus the geometric isotope effects. In particular, it is found that the hydrogen bonds are cooperative, that is, both expand simultaneously even in the case of an asymmetric isotopic substitution. The theoretical predictions compare favorably with NMR chemical-shift data.     

Microwave accelerated aza-Claisen rearrangements

The microwave-assisted thermal aza-Claisen rearrangement of allylic imidates and thiocyanates to the corresponding amides and isothiocyanates is investigated. Significant accelerations of the rearrangement of allylic imidates to amides and of allylic thiocyanates to isothiocyanates in comparison with standard thermal reactions is observed.     

Tandem asymmetric conjugate addition--silylation of enantiomerically enriched zinc enolates. Synthetic importance and mechanistic implications

[formula: see text] The zinc enolates, resulting from the copper-catalyzed enantioselective conjugate addition of dialkyl zinc reagents to cyclic and acyclic enones, could be trapped, quantitatively, as silyl enol ethers with TMSOTf in apolar solvents or with TMSCI and NEt3. These enantiomerically enriched silyl enol ethers were submitted to four synthetic transformations to show their synthetic utility. The zinc enolates obtained from acyclic enones were found to be configurationally stable, as shown by the stereochemistry of the silyl enol ethers.     

Rapid parallel synthesis of polymer-bound enones utilizing microwave-assisted solid-phase chemistry

A microwave-assisted parallel solid-phase synthesis of a collection of 21 polymer-bound enones has been developed. The two-step protocol involves initial high-speed acetoacetylation of polystyrene Wang resin with a selection of seven common beta-ketoesters. When microwave flash heating at 170 degreesC was employed, complete conversions were achieved within 1-10 min, a significant improvement over the conventional thermal method, which takes several hours for completion. Significant rate enhancements were also observed for the subsequent microwave-heated Knoevenagel condensations with a second set of 13 different aldehydes. Reaction times were reduced to 30-60 min at 125 degreesC in the microwave protocol compared to 1-2 days using conventional thermal conditions. Kinetic comparison studies indicate that the observed rate enhancements can be attributed to the rapid direct heating of the solvent (1,2-dichlorobenzene) by microwaves rather than to any specific microwave effect. All reactions have been carried out in commercially available parallel reactors with on-line temperature measurement, designed specifically for use in multimode microwave cavities.     

Adaptive Filtering Revisited

This paper shows that the adaptive filtering and forecasting techniques proposed by Makridakis and Wheelwright can be viewed as approximations to a more precise filtering method in which the Kalman filter is applied to a dynamic autoregressive model which is a special case of the models of Harrison and Stevens. The correct "learning" or "training factors" are shown to be data-dependent matrices rather than scalar constants.     

The ϕ 2 4 quantum field as a limit of Sine-Gordon fields

We exhibit the λ? ₂ ⁴ quantum field theory as the limit of Sine-Gordon fields as suggested by the identity $$\varphi ^4 /4! = \mathop {\lim }\limits_{\varepsilon \to 0} (\varepsilon ^{ - 4} \cos \varepsilon \varphi - \varepsilon ^{ - 4} + \tfrac{1}{2}\varepsilon ^{ - 2} \varphi ^2 ).$$ The proofs of finite volume stability for the two models, due to Nelson and Fröhlich respectively, are unrelated. We find a generalized stability argument that incorporates ideas from both of the simpler cases. The above limit, for the Schwinger functions, then proceeds uniformly in ?. As a by-product, let (?,dμ) be a Gaussian random field, ? _K (1≦κ<∞) a regularization of ?, andV a function satisfying:

1. V(? _K )≧?ak ^α
2. ∥V(?) ?V(? _K )∥ _p≦bp ^β k ^?γ, 2≦p < ∞

Thene ^?V(?)∈L ¹(dμ) provided α(β?1)<γ.     

The Robertson-Walker metric and the symmetries belong to the family of contracted Ricci collineations

It is shown that the general form of the Robertson-Walker cosmological metric admits symmetry properties that are members of the symmetry family of contracted Ricci collineations. A particular form for the conservation law generator given by _j [(–g)^1/2(T _i ^j –1/2 _i ^jT ) ⁱ ] = 0 following in consequence of these symmetries is obtained and interpreted.