Synthese von 3-(2-Carboxy-4-Pyridyl)- und 3-(6-Carboxy-3-pyridyl)-DL-alanin

Synthesis of 3-(2-Carboxy-4-pyridyl)-and 3-(6-Carboxy-3-pyridyl)-DL-alanine As starting materials for potential photochemical approaches to betalaines C(R = COOH) and to muscaflavine F(R = COOH), β-(2-carboxy-4-pyridyl)- and β-(6(carboxy-3-pyridyl))-DL-alanine ( A and D with R = COOH or 4 and 11 ), respectively, were prepared (Scheme 1). The synthesis of 4 (= A, R = COOH) started with the 2-[(4-pyridyl)methyl]malonate 1 and proceeded via the N-oxide 2 , cyanation and hydrolysis (Scheme 2). Amino acid 11 was obtained from (3-pyridyl)methyl-bromide ( 6 ) via the malonate 7 by an analogous sequence of reactions (Scheme 3).     

Bestimmung von Sauerstoff auf Al-Oberfl?chen durch R?ntgenspektralanalyse mit Prim?ranregung in Kombination mit einem Hei?extraktions-Verfahren

Zusammenfassung Die Röntgenspektralanalyse mit Elektronenstrahlanregung stellt eine leistungsfähige Methode zur Bestimmung von Sauerstoff auf metallischen Oberflächen dar, wenn man das Heißextraktions-Verfahren zur Eichung heranzieht. Dies wird am Beispiel von 99,5%igem Aluminium mit einem Oberflächen-Sauerstoffgehalt von ca. 0,5 g/cm² demonstriert. Die Ergebnisse stehen in guter Übereinstimmung mit denen der Deuteronenaktivierung.Wir danken Frau A. Kahles für ihre exakten Heißextraktionsanalysen und manche sachverständige Anregung sowie Frau Dr. D. Heesen für ihre Hilfe bei der Probenpräparation und den Messungen an der Makrosonde recht vielmals.     

Einige bestrahlungsexperimente mit 2, 1-Benzisothiazolen

Some Irradiation Experiments with 2, 1-Benzisothiazoles 2, 1-Benzisothiazole ( 1 ) on irradiation with a mercury high-pressure lamp in benzene/diethylamine yields, after acetylation, 2-acetylamino-benzaldehyde ( 3 ; Scheme 1). Similarly, irradiation of 3-chloro-2, 1-benzisothiazole ( 2 ) in benzene/diethylamine leads to a mixture of 3-dimethylamino-2, 1-benzisothiazole ( 6a ) and N, N-diethyl-thioanthranilamide ( 7a ; Scheme 2). Benzisothiazole 6a , on irradiation, is not transformed into 7a . On the other hand, when 2 is irradiated in methanol a mixture of 3-methoxy-2, 1-benzisothiazole ( 4a ) and methyl anthranilate ( 5a ; Scheme 2) is obtained. In this case, 4a on irradiation in methanol or ethanol also yields 5a . No exchange of the methoxy group in 4a is observed when the irradiation is performed in ethanolic solution. Thus, 2, 1-benzisothiazoles 1 , 2 and 4a react photochemically by N,S-bond cleavage and hydrogen-atom abstraction from the solvent (Scheme 3). 3-Chloro-2, 1-benzisothiazole ( 2 ) shows a second photoreaction, i.e. nucleophilic exchange of the chloro substituent by methanol or diethyl amine. The latter reaction can also be observed thermally, e.g. in boiling methanol in the presence of methoxide ions.     

Reaction of hydroxylamine with 5-aminooxazoles. A new route to isoxazoles

The nucleophilic attack of hydroxylamine at the 5 position of 2-aryl-4-trifluoroacetyl-5-amino-oxazoles leads to a mixture of stereoisomeric isoxazolines. Dehydration of these isomeric isoxazolines in the presence of trifluoroacetic anhydride gives 3-amino-4-acylamino-5-trifluoromethylisoxazoles. The structures and spectroscopic data of these compounds are discussed.     

Alkaline hydrolysis of 2-(trifluoromethyl)imidazo[4,5-f] and -[4,5-h]quinolines

2-(Trifluoromethyl)imidazo[4,5-$\text{f}$] and -[4,5-$\text{h}$]quinoline have been prepared from 5(6),acetamido-2-(trifluoromethyl)benzimidazole and 7,8-diaminoquinoline respectively. These (trifluoromethyl)- quinolines like 2-(trifluoromethyl)imidazoles but unlike 2-(trifluoromethyl) benzimidazoles, undergo hydrolysis in dilute sodium hydroxide to give ultimately the corresponding imidazo[4,5-$\text{f}$] and -[4,5-$\text{h}$]- quinoline, respectively.     

Über die Konfiguration des Prolins im Ergotamin

It is well known that in the ergot alkaloids of the peptide type the proline appears in thel-configuration. Different methods of acid hydrolysis may lead to various cleavage products; hydrolysis by HCl yieldsd-proline, on the other hand hydrolytic cleavage by means of strongly acid cation exchange resin preserved the orginall-configuration.

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Teilveröffentlichung der Dissertation vonH. Kolassa, Univ. Wien, 1973.     

Thermische Polymerisation von Acenaphthylen

Zusammenfassung Acenaphthylen wurde durch Anpolymerisation und zweifache Hochvakuumsublimation gereinigt. Die Reinigungsmethode wird ausführlich beschrieben.Bei verschiedenen Temperaturen wurde mit einer dilatometrischen Methode die thermische Bruttogeschwindigkeit gemessen. Zwischen 95 und 105 °C giltk _br=7,0₈·10¹⁰ exp (– 30,9 kcal/RT).Die beträchtliche Aktivierungsenergie der Bruttoreaktion ist sowohl auf eine große Aktivierungsenergie der thermischen Startreaktion als auch auf eine relativ hohe Wachstumsaktivierungsenergie zurückzuführen.Das Polymerisationsverhalten von Acenaphthylen kann vermutlich aufgrund seiner sterischen Eigenschaften erklärt werden.

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Summary Acenaphthylene was purified by partial polymerisation, followed by double stage high vacuum sublimation. The method of purification is described in detail.The thermal overall rate was measured at different temperatures by a dilatometric method. Between 95 and 105 °C the following relation holds:k _th=7,0₈ · 10¹⁰ exp (– 30,9 kcal/RT).The considerable energy of activation of the overall reaction depends on a relatively high energy of activation of both the thermal initiation and the propagation reaction.It is supposed, that the polymerisation behaviour of acenaphthylene depends mainly on its steric properties.

     

Unusual emissions from low-concentrated porphyrin solutions

This contribution presents fluorescence measurements from highly diluted tetratolylporphyrin (TTP) solutions where acetone has been chosen as solvent. The concentrations of the solutions ranged from 10(-8) to 10(-14) M. Apart the normal S1-S0 fluorescence a new broad emission was recorded below 10(-8) M. This new emission blue-shifted to the S1-S0 fluorescence covered the spectral range between 19000 and 14000 cm(-1). Within the dilution series, both the S1-S0 porphyrin fluorescence and the new emission exhibited a remarkably non-linear concentration-dependence. In the case in which the aggregate emission was strong, little S1-S0 emission could be detected and vice versa. The intensity maximum of the broad emission was detected from a 10(-13) M solution. The supplementary fluorescence was attributed to the presence of assembled molecules. This assumption was established by comparing the measurements with those obtained from 1:1 acetone water solvent mixtures in which the formation of aggregates had been formerly proven. The emission originating from the formation of aggregates was interpreted by a qualitative model considering the energy levels of J-aggregated porphyrins.     

Coleone C,D, I,I′ aus einer madegassischen Plectranthus sp. nov. Interkonversion von cis- und trans-A/B-6,7-Diketoditerpenen

Coleons C, D, I, I′, obtained from a Madagascan Plectranthus sp. nov.. Interconversion of cis- and trans-A/B-6,7-Diketoditerpenes. Fairly large amounts of Coleons C and D, as well as Coleons I and I′ (3-O-formyl derivative of Coleon I) can bc isolated from the orange glands of an unclassified North Madagascan Plectranthus sp. A reversible transformation of cis- and trans-A/B-6,7-dioxo-abietane via its diosphenol has been achieved for the first time. CD.-Spectra of these compounds are presented. Hydrogenolysis of Coleon D leads to 6β,16-dihydroxy-royleanone.     

Partialsynthese der Grandidone A, 7-Epi-A,B, 7-Epi-B,C, D und 7-Epi-D aus 14-Hydroxytaxodion

Partial Synthesis of Grandidones A, 7-Epi-A, B, 7-Epi-B, C, D and 7-Epi-D, from 14-Hydroxytaxodione Oxydative addition of coleon U ( 6 ) to 14-hydroxytaxodione ( 5 ) in the presence of Fétizon's reagent mainly leads to grandidone A ( 1a ) and 7-epigrandidone A ( 1b ) (ca. 15:1), whereas coleon V ( 7 ) and 5 under the same conditions yield grandidone B ( 2a ) and 7-epigrandidone B ( 2b ) (ca. 3:1). Dimerization of 14-hydroxytaxodione ( 5 ) gives grandidone C ( 3 ; ca. 40%), grandidone D ( 4a ; ca. 50%) and 7-epigrandidone D ( 4b ; ca. 10%). All these compounds obtained by partial synthesis are in every respect identical with the natural products, thus establishing their absolute configurations. The thermal transformation of grandidone C ( 3 ) to grandidone D ( 4a )/7-epigrandidone D ( 4b ) and interconversions of 4a and 4b were achieved. Oxydative addition of coleon U ( 6 ) to 14-hydroxytaxodione ( 5 ) in the presence of Fétizon's reagent mainly leads to grandidone A ( 1a ) and 7-epigrandidone A ( 1b ) (ca. 15:1), whereas coleon V ( 7 ) and 5 under the same conditions yield grandidone B ( 2a ) and 7-epigrandidone B ( 2b ) (ca. 3:1). Dimerization of 14-hydroxytaxodione ( 5 ) gives grandidone C ( 3 ; ca. 40%), grandidone D ( 4a ; ca. 50%) and 7-epigrandidone D ( 4b ; ca. 10%). All these compounds obtained by partial synthesis are in every respect identical with the natural products, thus establishing their absolute configurations. The thermal transformation of grandidone C ( 3 ) to grandidone D ( 4a )/7-epigrandidone D ( 4b ) and interconversions of 4a and 4b were achieved. Oxydative addition of coleon U ( 6 ) to 14-hydroxytaxodione ( 5 ) in the presence of Fétizon's reagent mainly leads to grandidone A ( 1a ) and 7-epigrandidone A ( 1b ) (ca. 15:1), whereas coleon V ( 7 ) and 5 under the same conditions yield grandidone B ( 2a ) and 7-epigrandidone B ( 2b ) (ca. 3:1). Dimerization of 14-hydroxytaxodione ( 5 ) gives grandidone C ( 3 ; ca. 40%), grandidone D ( 4a ; ca. 50%) and 7-epigrandidone D ( 4b ; ca. 10%). All these compounds obtained by partial synthesis are in every respect identical with the natural products, thus establishing their absolute configurations. The thermal transformation of grandidone C ( 3 ) to grandidone D ( 4a )/7-epigrandidone D ( 4b ) and interconversions of 4a and 4b were achieved. Oxydative addition of coleon U ( 6 ) to 14-hydroxytaxodione ( 5 ) in the presence of Fétizon's reagent mainly leads to grandidone A ( 1a ) and 7-epigrandidone A ( 1b ) (ca. 15:1), whereas coleon V ( 7 ) and 5 under the same conditions yield grandidone B ( 2a ) and 7-epigrandidone B ( 2b ) (ca. 3:1). Dimerization of 14-hydroxytaxodione ( 5 ) gives grandidone C ( 3 ; ca. 40%), grandidone D ( 4a ; ca. 50%) and 7-epigrandidone D ( 4b ; ca. 10%). All these compounds obtained by partial synthesis are in every respect identical with the natural products, thus establishing their absolute configurations. The thermal transformation of grandidone C ( 3 ) to grandidone D ( 4a )/7-epigrandidone D ( 4b ) and interconversions of 4a and 4b were achieved.