Synthese und Reaktionen desDiels-Alder-Addukts aus Pyren und Hexachlorcyclopentadien

TheDiels-Alder adduct2 from pyrene and hexachlorocyclopentadiene exhibits a different substitution pattern than pyrene itself, namely that of phenanthrene. By reactions with the adduct following Retro-Diels-Alder splitting, pyrene substitution products are accessible that cannot be obtained by direct substitution of pyrene. This is demonstrated by the synthesis of 4-chloropyrene (5) and 4-bromopyrene (6).

Herrn Prof. Dr.Oskar E. Polansky zum 60. Geburtstag gewidmet.     

Synthesis of novel tryptamine and β-carboline derivatives via palladium-catalyzed reaction of bromotryptamine with organic boronic acids

New tryptamine 5, 7 and β-carboline derivatives 3 were preparated by palladium-catalyzed coupling reaction of 5-bromotryptamine 1 with aryl boronic acids. Dedicated to Professor András Lipták on his 70^th birthday.     

Darstellung,Struktur und Reaktionsfähigkeit von Metallderivaten des 1-Propinphosphonsäure-diethylesters

Metallation of diethyl ester of 1-propynephosphonic acid (1-DEPP) is achieved by treatment with alkaline amides, calcium amid and calcium in liquid ammonia, with isopropylmagnesium chloride in ether or via metal exchange from the potassium derivative of 1-DEPP with copper(II) and cobalt(II) chloride resp.On the basis of IR-and¹H-NMR-spectra the calcium derivative appears as a mixture of an allene and its isomeric acetylene. The IR-spectrum of the lithium derivative is consistent with an analogous phenomenon while an acetylene structure is attributed only to the cobalt and copper derivatives. The alkylation of the potassium derivative with alkyl halides and the hydroxy-alkylation with benzaldehyde occur with low yield at the -position of the parent compound.

     

Zur Synthese von Norbornanonen mit geminaler Dimethylgruppe

The synthesis ofgem-dimethylnorbornanones is described. One synthetic pathway after aDiels-Alder reaction involves the transformation of the nitro group into the oxo group with subsequent methylation into the geminal dimethyl product. A shorter way by [4+2]-cycloaddition of cyclopentadiene with a suitable dimethylated dienophile (e.g. 2-methyl-1-nitropropene) failed, probably by steric hindrance of the dienophile. 7-Oxanorbornanones, with agem-dimethyl group could not be prepared. A second synthetic approach togem-dimethylnorbornanones is opened byLewis acid catalyzed rearrangement of cyclohexenylcarbaldehydes.

Herrn Univ.-Prof. Dr.K. Kratzl mit den besten Wünschen zum 65. Geburtstag gewidmet.     

Michael reaction. V. Stereochemistry of the NaNH2 catalyzed two-step reaction between phenylacetic acid dialkyl amides and methyl cinnamate or cinnamic acid dialkyl amides

The reaction is investigated between sodium-metallated (NaNH₂) phenylacetic acid dialkyl amides and methyl cinnamate or cinnamic acid dialkyl amides. The thermodynamic equilibrium between the diastereomeric 2,3-diphenylglutaric acid amidoesters or diamides is 5/95 in favour of thethreo-isomer. Under kinetic conditions the stereochemistry of the reaction depends on the nature of the donor and the solvent.

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Michael Reaktion. V. Stereochemie der durch NaNH₂ katalysierten zweistufigen Reaktion zwischen Dialkylamiden der Phenylessigsäure und Methylestern oder Dialkylamiden der Zimtsäure

Zusammenfassung Die Umsetzung zwischen der mit festem NaNH₂ gewonnenen Natriumderivaten der Dialkylamiden der Phenylessigsäure und Methylestern oder Dialkylamiden der Zimtsäure wurde untersucht. Das thermodynamischeE/T-Verhältnis zwischen den gewonnenen diastereomeren Amidestern und Diamiden der 2,3-Diphenylglutarsäure beträgt in allen Fällen 5/95. Das stereochemische Ergebnis unter kinetischen Bedingungen hängt von der Natur des Donators und von den Lösungsmitteln ab.

     

Zur Konstitutionsaufklärung trisubstituierter Indolderivate: NMR-spektroskopische Untersuchung von Bis(2,3-dimethyl-6-indolyl)-arylmethanen

The application of combined¹H- and¹³C-NMR-technics is used exemplarily for the elucidation of the type of substitution at the phenyl nucleus of indoles in 6,6-bis-indolylarylmethanes (1,2). These methods can be applied in general to analogous structure problems.

     

A convenient synthesis of linear pyranocoumarins. Xanthyletin and 3-Phenylxanthyletin

A convenient synthesis of linear pyranocoumarins, viz., 8,8-dimethyl-2H,8H-benzo[1,2-b; 5,4-b]dipyran-2-one (xanthyletin,1) and 8,8-dimethyl-3-phenyl-2H,8H-benzo[1,2-b; 5,4-b]dipyran-2-one (3-phenylxanthyletin,2) is described. The key steps are blocking the 8-position of appropriate 7-hydroxy-2H-1-benzopyran-2-one derivatives with iodine and 1,1-dimethyl-2-propynylation followed by cyclisation.

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Ein einfacher Syntheseweg zu linearen Pyranocumarinen. Xanthyletin und 3-Phenylxanthyletin

Zusammenfassung Es wird ein vorteilhafter Weg zur Synthese von linearen Pyranocumarinen am Beispiel von Xanthyletin und 3-Phenylxanthyletin gezeigt. Das Syntheseprinzip besteht in einer Blockierung der 8-Position des entsprechenden 7-Hydroxy-2H-1-benzopyran-2-ons mit Jod und einer 1,1-Dimethyl-2-propinylierung mit nachfolgender Cyclisierung.

     

Synthese von Benzofuranen durch Cyclodehydrierung von Phenylmalonylheterocyclen

Phenylmalonyl heterocyclic compounds such as the quinolones1a–c or3, benzoquinolizinones6a, b and the phenalenones8a, b can be converted to benzofuranes (2a–c, 7a, b and9a, b) by cyclodehydrogenation with Pd/C in boiling diphenyl ether. 2-Phenylchinchonic acid (10) reacts under the same conditions to the dimeric benzofuroquinoline12: the decarboxylated quinoline11 however gives the monomer13.

Herrn Prof. Dr.G. Zigeuner zur Vollendung seines 60. Lebensjahres gewidmet.     

Zur Synthese von β-Isosantalol

The synthesis of a new allylic alcohol with a norbornane skeleton is described. The convergent synthesis leads from 3-methylene-norbornan-2-one to -isosantalol (6). An important structural parameter of6 is derived from -Santalol (1), the main constituent of east indian sandalwoodoil with a powerful woody fragrance. Another structural parameter of6 is derived from isosantalol (3) with a weak woody odour. The odour of the new alcohol6 is weaker than that of3, probably because of too much osmophoric groups and a very reactivecis-1,3-butadiene-system. Another possible route to6 by means of aWittig-reaction did not succed.

Teil der Diplomarbeit vonM. Wiedenhorn, Universität Wien, 1980.     

Knoevenagel Reaction of malononitrile and its “dimer” with β-ketoanilides

The reaction of benzoylacetanilides with malononitrile has been investigated. The structure of the compounds obtained (2, 3, 4) have been assigned on the basis of chemical properties and spectral data.

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Die Knoevenagel-Reaktion von Malodinitril und seinem Dimer mit -Ketoaniliden

Zusammenfassung Die Reaktion von Malodinitril mit Benzoylacetaniliden wurde untersucht. Die Struktur der dabei erhaltenen Verbindungen (2–4) wurde auf Basis der chemischen und spektroskopischen Eigenschaften zugeordnet.

     

Zur Darstellung sechsgliedriger Cyclosilane mit einem Heteroatom

In the nearly unknown class of cyclosilanes with one heteroatom, decaphenyl-oxa-cyclohexasilane was prepared for the first time by removing of water. The diol was prepared by hydrolysis of the corresponding 1,5-dichlorocompound. Cyclisation was not successful with 1,5-Di(ethylamine)decaphenylpentasilane, which was prepared also for the first time. Spectroscopic data were determined of all synthesized compounds.

Herrn Prof. Dr.G. Zigeuner zum 60. Geburtstag gewidmet.     

Synthese und Fluoreszenzeigenschaften von cyansubstituierten 2-Aminopyridinen

The synthesis of several 2-aminopyridines is described. The reaction of tetracyanoethylene with 3-imino-propane-carbonitrile gives 2-amino-3,4,5-tricyano-pyridines with alkyl and aryl-substituents, resp., in position 6. Nucleophilic substitution of 2-amino-6-chloro-3,5-dicyanopyridines and 2-amino-6-chloro-3,4,5-tricyano-pyridines with phenolates leads to a variety of pyridines. Spectroscopical data of absorption and fluorescence are presented and the influence of the cyano groups is discussed. The results are in good agreement with quantum chemical calculations (PPP).

Herrn Univ-Prof. Dr.A. Holasek zum 60. Geburtstag gewidmet.     

Über die Kinetik der durch Schwefelsäure katalysierten Reaktion von Chloral und Benzol

The kinetical parameters of 1-phenyl-1-hydroxy-2,2,2-trichloro-ethane and 1,1-diphenyl-2,2,2-trichloro-ethane production and the simultaneous sulphonation reaction were determined, taking into account the alteration of the reaction rate constants caused by the dilution of the sulphuric acid catalyst.

     

Neue Synthesemethoden 1 Einfache Synthese von Thiolestern

A new and simple synthesis of thiolester by reaction of the mixed anhydrides1 with alkalisalts of mercaptanes and thiophenolates is presented.

     

Zur Synthese von Human-Big-Gastrin I

The synthesis of the tetratriacontapeptide amide corresponding to the revised primary structure of human big gastrin I is described. For this purpose the fragments were designed in view of the maximum use of those utilized in our previous synthesis of human big gastrin I according to the first sequence proposal. Consequently the key tripeptide-Pro-Pro-His- (sequence 7–9) was prepared in suitably protected form to be used as amino or carboxyl component for assembly of the segments 1–9 and 1–14, respectively. Final condensation of the latter nona- and tetradecapeptide derivatives with the C-terminal segments 10–34 and 15–34 via the azide and the dicyclohexylcarbodiimide/N-hydroxysuccinimide procedure, respectively, leads to crude fully protected human big gastrin I. Upon deprotection by exposure to trifluoroacetic acid in presence of ethanedithiol-(1,2) as scavanger, ion exchange chromatography and partition chromatography, the desired tetratriacontapeptide amide was isolated in satisfactory yield with a high degree of purity. The identical immunological behaviour of the synthetic material, if compared with that of natural human big gastrin I, represents ulterior strong evidence for the correctness of the newly proposed structure for this putative prohormonal form of the gastrins.

Kurzmitteilung:Wünsch E., Wendlberger G., Mladenova-Orlinova L., Göhring W., Jaeger E., Scharf R., Gregory R. A., Dockray G. J., Hoppe-Seyler's Z. Physiol. Chem.362, 179 (1981).     

Eine effiziente Synthese von Aminoalkylidenderivaten fünfringcyclischer methylenaktiver Verbindungen

Trimethyl orthoacetate, orthopropionate or orthobenzoate in contrast to orthoformiate do not undergo a three component condensation with anilines and cyclic sixmembered active methylene compounds to the corresponding N-substituted aminomethylene derivatives; they do react, however, with five membered ring compounds. The reaction proceeds smoothly with primary aliphatic or aromatic amines, whilst secondary amines give no or only low yields. In comparison to other synthetic routes to ,-diacyl-enamines the condensation described has the following advantages: a) The products thus obtained have previously often required a two step procedure, b) the only reaction product besides the aminoalky lidene derivative is an alkohol, c) the usually mild conditions allow the preparation of compounds so far not available by employing more drastic alternative methods.

5. Mitt.:Wolfbeis, O. S., Junek, H., Mh. Chem.110, 1387 (1979).     

Kinetische Untersuchungen über die Silicium—Aryl-Spaltung mit Bromwasserstoff

Rate constants of the cleavage reaction of silicon aryl linkages with HBr were estimated for various aryl derivatives by means of NMR. A row of substituents was obtained, dependent on the cleavage rates. Correlation with theHammett function shows the electrophilic character of the reaction. The different cleavage rates give the possibility for specific cleavages of aryl groups from silanes.

     

Synthesis of some new fluorine containing 3-dialkylaminomethyl indoles, 3-indolylglyoxamides and tryptamines

Several new 2-(fluoroaryl)-3-dialkylaminomethylindoles, 3-acetyl-2-(fluoroaryl)-indoles, 2-(fluoroaryl)-3-indolylglyoxamides and corresponding tryptamines have been prepared as possible psychopharmacological agents. 2-(Fluoroaryl)-indoles have been synthesized by theFischer indole synthesis. 2-(Fluoroaryl)-indoles on treatment with oxalyl chloride and subsequent reaction with amines, gave 2-(fluoroaryl)-3-indolylglyoxamides. Some of these indolylglyoxamides were reducted with lithium aluminium hydride, to the corresponding tryptamines. 2-(Fluoroaryl)-indoles when subjected toMannich reaction afforded 3-dialkylaminomethyl-2-(fluoroaryl)-indoles. All these new compounds have been characterized by IR spectral studies.Possible Psychopharmacological Agents, Part XII, Part XI, J. Indian. Chem. Soc.57, 423 (1980).     

Thiophen-sulfoxide

The synthesis of several 5-methylsulfinyl-2-thiophenaldehyde derivatives is described.

     

Synthese von Indolen und Isochinolonen aus Phenylmalonylheterocyclen

A new synthesis of the indole system has been achieved by chclodehydrogenation of amino phenylmalonate heterocycles. Thus, the 4-amino coumarins1 a,b or the 4-amino-2-quinolones1 c–g are converted to the indoles2 with palladium on charcoal in boiling diphenyl ether. The reaction of the aminocompounds1 with diphenyl carbonate yields the fused polycyclic isoquinolones4.