Herstellung von Hilfsstoffen für die asymmetrische Synthese aus Weinsäure. Addition von Butyllithium an Aldehyde in chiralem Medium

Preparation of Auxiliaries for Asymmetric Syntheses from Tartaric Acid. Additions of Butyllithium to Aldehydes in Chiral Media. Chiral derivatives of the complexing 1,2-diheterosubstituted ethanes A–D are prepared from tartaric acid. The key starting materials are the succinic acid derivative 1 , the dioxolane 2a , and the diamide 3a . These are converted to the ethers, alkoxyamines, and alkylthio-amines listed in the first column of Table 2 which also contains the derivatives 21c, 22d , and 23d made from lactic acid, malic acid, and proline, respectively. It is shown that the highest optical yields (up to 40%) in reactions of butyllithium with aldehydes are obtained when mixtures of (?)-1,2,3,4-tetramethoxy-butane ( 4b ), (+)-2,3-dimethoxy-N,N,N′,N′-tetramethyl-1,4-butanediamine ( 17a ), and (?)-1,4-dimethoxy-N,N,N′,N′-tetramethyl-2,3-butanediamine ( 14c ) with pentane are used at temperatures down to ?150° and ratios of auxiliary/butyllithium of up to 10:1 (see equation (1), Tables 2–4).     

Einflüsse der Lösungsmittel auf das ESR-Spektrum von Kupfer-acetylacetonat

Effect of 11 inert solvents (carbon tetrachloride, nitrobenzene, acetonitrile, sulpholane, propylene carbonate, acetone, ethyl acetate, tetrahydrofuran, dimethylformamide, dimethylsulfoxide and hexamethylphosphoramide) on the ESR spectrum of copper acetylacetonate have been studied at the temperature about 298 K. There was stated that hyperfine splitting linearly decreases with the increasing ofGutmann's donor number of solvent. This phenomenon was discussed in terms of solvent—solute interaction.

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Mit 2 Abbildungen     

13 C-NMR-untersuchungen an substituierten cycloalkenen : I. Trimethylsilylenolether

The ¹³C-NMR spectra of the cyclic silyenolethers 1a-i are discussed with regard to the electron density within the carbon ring skeleton, conformation of the trimethylsilyloxy substituent and configuration of the double bond in higher membered ringsystems.     

Parametric wave interaction in one-dimensional nonlinear photonic crystal with randomized distribution of second-order nonlinearity

We theoretically study the parametric wave interaction in nonlinear optical media with randomized distribution of the quadratic nonlinearity $\chi ^{(2)}$ . In particular, we discuss the properties of second and cascaded third harmonic generation. We derive analytical formulas describing emission properties of such harmonics in the presence of $\chi ^{(2)}$ disorder and show that the latter process is governed by the characteristics of the constituent processes, i.e. second harmonic generation and sum frequency mixing. We demonstrate the role of randomness on various second and third harmonic generation regimes such as Raman?CNath and ?erenkov nonlinear diffraction. We show that the randomness-induced incoherence in the wave interaction leads to deterioration of conversion efficiency and angular spreading of harmonic generated in the processes relying on transverse phase matching such as Raman?CNath interaction. On the other hand, the ?erenkov frequency generation is basically insensitive to the domain randomness.     

Electrostatic potentials of molecules and prediction of the lewis acid-base properties of solvents,part II. Application of electrostatic parameters

Summary Electrostatic parameters,UN andUP, introduced previously, have been applied to predict solvent acid and base properties. TheUN parameter correlates well with the electrostatic component of solvent basicity. This parameter also significantly improves correlations between Koppel-Paju, Kamlet-Taft and Gutmann basicity scales. TheUP parameter combined with Mullikan charges at hydrogen atoms of the solvent molecules allows an estimation of solvent acidity parameters in the frame of the two-parameter similarity model. The results show that parameters computed with the MNDO method for isolated molecules are suitable for molecules of nonaqueous solvents in liquid state.

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Elektrostatische Potentiale von Molekülen und Voraussage von Lewis-Säure-Base-Eigenschaften von Lösungsmitteln, 2. Mitt.: Anwendung elektrostatischer Parameter

Zusammenfassung Die in der vorhergehenden Arbeit eingeführten elektrostatischen ParameterUN undUP wurden zu Vorhersagen von Säure- und Base-Eigenschaften von Lösungsmitteln angewandt. DerUN-Parameter korreliert gut mit der elektrostatischen Komponente der Lösungsmittelbasizität und verbessert auch signifikant Korrelationen zwischen der Koppel-Paju, Kamelt-Taft und Gutmann'schen Basizitätsskala. DerUP-Parameter, in Kombination mit Mullikan-Ladungen an den Wasserstoffatomen der Lösungsmittelmoleküle, erlaubt die Abschätzung von Solvens-Aciditäts-Parametern im Rahmen eines Zweiparameter-Vergleichsmodells. Die Ergebnisse zeigen, daß die über die MNDO-Methode für isolierte Moleküle berechneten Parameter zur Beschreibung von nichtwäßrigen Lösungsmitteln geeignet sind.

     

Isomerization and Decomposition of a Criegee Intermediate in the Ozonolysis of Alkenes: Dynamics Using a Multireference Potential

The isomerization and decomposition dynamics of the simplest Criegee intermediate CH₂OO have been studied by classical trajectory simulations using the multireference ab initio MR‐PT2 potential on the fly. A new, accelerated algorithm for dynamics with MR‐PT2 was used. For an initial temperature of 300 K, starting from the transition state from CH₂OO→CH₂O₂ , the system reaches the dioxirane structure in around 50 fs, then isomerizes to formic acid (in ca. 2800 fs), and decomposes into CO+H₂O at around 2900 fs. The contributions of different configurations to the multiconfigurational total electronic wave function vary dramatically along the trajectory, with diradical contributions being important for transition states corresponding to H‐atom transfers, while being only moderately significant for CH₂OO. The implications for reactions of Criegee intermediates are discussed.