Über die Reaktion von Äthylketencarbonsäure-äthylester mit Benzalanilin

Zusammenfassung Dem vonStaudinger aus Äthylketencarbonsäureäthylester und Benzalanilin bei –20° dargestellten Addukt kommt die offenkettige, zwitterionische Struktur eines 4-Äthoxycarbonyl-1,2-diphenyl-2-azonia-1,3-hexadien-3-olats (3) zu.

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Reaction of ethyl 2-ethylketenecarboxylate with benzylidene aniline

The adduct obtained byStaudinger at –20° from ethoxycarbonyl ethyl ketene and benzylidene aniline has the open chain dipolar structure of 4-ethoxycarbonyl-1,2-diphenyl-2-azonia-1,3-hexadien-3-olate (3).

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Über die Thermolyse disubstituierter Malonylchloride

Zusammenfassung IR-spektroskopische Untersuchungen an disubstituierten Malonsäurechloriden haben ergeben, daß die Thermolyse—im Gegensatz zu der von monosubstituierten Malonsäurechloriden—je nach Substituenten am mittelständigen C-Atom der Malonsäure zu unterschiedlichen Produkten führt.

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Thermolysis of disubstituted malonyl chlorides

It has been shown by infrared spectroscopic data that disubstituted malonyl chlorides do not react uniformly. This is in contradiction to the mode of reaction of monosubstituted malonyl chlorides.

     

Effect of polarization on population transfer in H2 by stimulated Raman transition with partially overlapping laser pulses

Polarization effects on population transfer by stimulated Raman transition using overlapping time dependent pump and Stokes laser pulses from the ground X ¹Σ _g ^/+ (v _g=0, J _g=1) level of H₂ to the final X ¹Σ _g ^/+ (v _f=1, J _f=1) level via the intermediate B ¹Σ _u ^/+ (v _i=14, J _i=0,2), C ¹Π _u ^/+ (v _i=3, J _i=2) and C ¹Π _u ^/− (v _i=3, J _i=1) levels have been theoretically investigated by applying the density matrix formalism. We have studied in detail the dependence of the population transfer on time delay between two pulses for the cases of on-resonance excitations considering linear parallel and same-sense circular polarizations of the fields. The pump and Stokes fields are taken as having Gaussian pulse shapes with peak intensities I _P ^/0 (I _S ^/0 )=2 × 10⁶ and 1 × 10⁷ W/cm². Density matrix equations have been solved for each value of the magnetic quantum number M _g(0, ±1) of the initial ground level taking into account the M _g dependence of the Rabi frequencies. M _g — averaged population transfer to the final level has also been calculated. For resonance excitations to the B(14, 0) or C(3, 1) levels, appreciable population transfer is achieved for intuitive pulse order for some particular values of M _g and M _i (magnetic quantum number of the resonant intermediate level) depending on the nature of polarizations. The calculated values of M _g — averaged population transfer for the two cases of polarizations show that for on-resonance excitation to the B(14, 0) or the C(3, 1) level, linear parallel polarization of the laser fields yield more transfer efficiency whereas for resonance excitation to the B(14, 2) level, larger population transfer results from the same-sense circular polarizations. For resonance excitation to the C(3, 2) level, M _g — averaged population is found to be almost polarization independent. The calculations for the six-level H₂ system reveal some interesting features of polarization effects on the population transfer efficiency.     

Highly enantioselective transfer hydrogenation of fluoroalkyl ketones

[Structure: see text] The asymmetric transfer hydrogenation of fluoroalkyl ketones mediated by [Ru(eta6-arene)((S,S)-R2NSO2DPEN)] catalysts using HCO2H-Et3N afforded the corresponding alcohols with high ee's and in excellent yields.     

5-Deoxy-5-Fluoro-D-Glucofuranose and -L-Idofuranose Synthesis and NMR Studies

Starting from 1,2-O-isopropylidene-α-D-gluco- and -β-L-ido-furanurono-6,3-lactone, 5-deoxy-5-fluoro-α/β-D-gluco- and -L-idofuranose, respectively, were prepared by the following sequence of reactions: trifluoromethanesulfonylation, nucleophilic substitution with inversion of configuration, lactone reduction and deprotection. On the basis of H-H-, H-C-, H-F-, and C-F-couplings, the stereochemistry of the products is discussed.     

THE SINGULARLY PERTURBED NONLOCAL REACTION DIFFUSION SYSTEM

In this paper the singularly perturbed initial boundary value problems for the nonlocal reaction diffusion system are considered. Unsing the iteration method and the comparison theorem, the existence, uniqueness and its asymptotic behavior of solution for the problem are studied.     

Synthesis and ring transformation of novel tetracyclic fused as-triazines

Summary Eight new tetracyclic fused as-triazines (4–6,8,11–13, and15) have been synthesized by conversion and subsequent ring transformation of 1,2-diaminoisoquinolinium (2) and -quinolinium salts (9) with 4-benzoyl-5-phenylfuran-2,3-dione (1). Selective alkylations of the new products revealed that these reactions are governed mainly by the electronic density of the lone pairs as well as by steric effects.Dedicated to em. Univ. Prof. Dr. E. Ziegler on the occasion of his 80th birthday     

Synthesen mit Nitrilen, 85. Mitt.: Über 4-Dicyanmethylen-und 4-Tricyanpropyliden-homophthalimide

Summary Addition of tetracyanoethylene to the 1,2,3,4-tetrahydro-isoquinoline-1,3-diones1 a–d yields 4-(dicyanomethylene)-1,2,3,4-tetrahydro-isoquinoline-1,3-diones3 or 4-(2-amino-1,1,3-tricyano-3-propylidene)-1,2,3,4-tetrahydro-1,3-diones4 depending on the substituent in position 2. Spectra of both types of derivatives are discussed.

     

Effect of substitution of Ce on superconducting properties of Bi1.7Pb0.3Sr2Ca2−x Ce x Cu3O10+δ system

We have investigated the superconducting properties of the Bi_1.7 Pb_0.3Sr₂Ca_2−xCe _x Cu₃O_10+δ system with x=0.00, 0.02, 0.04, 0.08 and 0.1 by X-ray diffraction and magnetic susceptibility. The substitution of Ce for Ca has been found to drastically change the superconducting properties of the system. X-ray diffraction studies on these compounds indicate decrease in the c-parameter with increased substitution of Ce at Ca site and volume fraction of high T _c (2 : 2 : 2 : 3) phase decreases and low T _c phase increases. The magnetic susceptibility of this compound shows that the diamagnetic on set superconducting transition temperature (onset) varies from 109 K to 51 K for x=0.00, 0.02, 0.04, 0.08 and 0.1. These results suggest the possible existence of Ce in a tetravalent state rather than a trivalent state in this system; that is, Ca²⁺ → Ce⁴⁺ replacement changes the hole carrier concentration. Hole filling is the cause of lowering T _c of the system.     

Zur Bildung von Mercaptursäuren bei der Entgiftung von 1,1-Diäthoxy-4-hydroxy-2-penten

Zusammenfassung Injiziert man Ratten i. p. 1,1-Diäthoxy-4-hydroxy-2-penten, so wird die Verbindung rasch resorbiert und metabolisiert. Im Harn können 6 Metaboliten nachgewiesen werden. Zwei davon wurden als diastereomere Mercaptursäuren identifiziert, nämlich als die N-Acetyl-S-(d-bzw.l-1-diäthoxymethyl-3-oxobutyl)-l-cysteine. Der Bildungsweg dieser Verbindungen wird besprochem.

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Mercapturic acid formation during detoxication of 1,1-diethoxy-4-hydroxy-2-pentene

Following intraperitoneal administration to rats 1.1-diethoxy-4-hydroxy-2-pentene is rapidly resorbed and metabolized. Among six metabolites excreted in rat urine two have been identified as the diastereomeric mercapturic acids, N-acetyl-S-(d-1-diethoxymethyl-3-oxo-butyl)-l-cysteine and N-acetyl-S-(l-1-diethoxymethyl-3-oxobutyl)-l-cysteine. The metabolic formation of these compounds is discussed.

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Herrn Prof. Dr. Dr. h. c.Otto Kratky mit den besten Wünschen zum 70. Geburtstag gewidmet.