neue Heterocyclisierungen mit Malonestern 1,3-Dithiole; 1,3-Oxathiole; Δ2-Oxazoline und das Vinylendipyridiniumdikation

The reaction of diethyl bromomalonate (1) or diethyl diazomalonate (6) with benzoyl isothiocyanate (2) proceeds via the carbene intermediates4, 7 or12 to afford the 1,3-dithiole5, the 2-oxazoline8 or the 1,3-oxathioles9 depending upon the catalyst employed. In contrast, the bis(ethoxycarbonyl)methylpyridinium bromides14 upon treatment with benzoyl isocyanates15 in pyridine give rise to vinylene dipyridinium dibromides18.

     

NMR-spektroskopische und massenspektrometrische Untersuchung der Struktur und Lösungsgleichgewichte von Hydroxyethylaminotoluchinonen

Summary The constitution of hydroxyethylaminotoluquinones have been assigned by means of modern NMR-techniques. The solution equilibria constants have been determined by recording¹H-NMR spectra at different temperatures. The reaction of compounds2a ₁ and2c ₁ with acetic anhydride leads to the corresponding acetyl derivatives with quinone skeleton. The mass spectra of2a ₁ –c ₁ are discussed on basis of the fragmentation pattern.

     

Synthese von 4-Acetoxy-1-aryl-2-azetidinonen

The 4-carboxy-2-azetidinones1 a,1 b und1 c react with leadtetraacetate/pyridine to give the 4-acetoxy-1-aryl-2-azetidinones2 a, 2 b and2 c. Hydrogenolysis of2 a yields2 d.

     

Bestimmung des Palladiums als Pyridinrhodanid und Pyridindichromat

Zusammenfassung Eine gewichtsanalytische Schnellbestimmung von Pd²⁺ mit Pyridinrhodanid und Pyridindichromat wird beschrieben. Dauer der Bestimmung etwa 30 Minuten. Versuche zur Fällbarkeit verschiedener Metalle mit Pyridin bzw. zwei Pyridinderivaten und verschiedenen Anionen führen zum Teil zu quantitativen Abscheidungen.

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Summary A rapid gravimetric determination of Pd²⁺ by means of pyridine thiocyanate and pyridine dichromate is described. The determination requires about 30 minutes. Trials of the precipitability of various metals with pyridine and two pyridine derivatives respectively, and various anions led in part to quantitative precipitations.

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Résumé On décrit un dosage pondéral rapide de Pd²⁺ par le thiocyanate et le bichromate de pyridinium. Le dosage demande environ 30 minutes. Les expériences sur la précipitabilité de divers métaux et anions par la pyridine et par deux dérivés de la pyridine conduisent en partie à des séparations quantitatives.

     

Synthese und Reaktivität von 2- und 3-hydroxylierten Dihydro-1,4-Benzoxazinen

2 can be pyrrolized to yield3 a, which in turn may be hydrolyzed with HCl to3 b. Acetylation of3 a followed by a reaction with trifluoroacetic acid (TFA) gives3 e. Elimination of ethanol from3 a or of water from3 e is not possible. Treatment of1 a with pyridine/acetic anhydride andTFA or with acetic acid/acetic anhydride affords4 a and4 b, resp. Reaction of4 b in benzene/p-toluenesulfonic acid for 2 hours yields both ethers5I and5II, whereas after 6 hours 4-acetyl-4H-1,4-benzoxazine (6) is obtained. The structures of all products are established by chemical and spectroscopic methods.

Teile aus der DissertationW. Kropp, Universität Wien, 1977.     

Zur Kenntnis der Reaktionsfähigkeit des 5-Methyl-4-ethyl-2-propanonyl-thiazols

The methylene group of 5-methyl-4-ethyl-2-propanonyl-thiazol (II) reacts with different aldehydes yielding theKnoevenagel-condensation products (1–14). The reactions ofII with amines or ammonia gives exclusively the enamines as demonstrated by the¹H-NMR-spectrum (15–23). The reaction product fromII with ammonia (23) can be further transformed to the corresponding derivatives of urea (24–27) with isocyanates.II reacts with acylchlorides in pyridine to the 0-acylation compounds (28–32) and with isocyanates to the corresponding urethanes (38–40).

     

Synthesen mit Nitrilen,LXXV Zur Reaktivität der Dimeren von Malononitril und Cyanessigester gegenüber Dimethylformamid-dimethylacetal

Reaction of malononitrile dimer (1) and the codimer from cyanoacetate and malononitrile (2) with dimethylformamide-dimethylacetal (DMFDMA) leads to the monocondensation products5 a, b. The isomeric codimer3, however, gives the amidine6. Ring closure reactions of5 a with ammonia and primary aliphatic and aromatic amines yield 2,4-diamino-3,5-pyridinedicarbonitriles7 a–j, in the case of5 b the 4-amino-1,2-dihydro-2-oxo-3,5-pyridinedicarbonitriles8 b–i. Reactions of1 and2 with an excess ofDMFDMA give the biscondensation products11 a, 11 b.11 b reacts with primary aromatic amines to give the pyridine derivatives13. The structure of13 was confirmed by hydrolytical cleavage to the dicyano-aminopyridone14. Treatment of13 with concentrated hydrochloric acid leads to the pyridopyrimidine derivatives15.

     

Reaktion von primären Alkylhydroperoxiden mit Amidoschwefelsäurechlorid: Alkyl(amidosulfonyl)peroxide

The novel peroxides H₂NSO₂OOCH₂ R (1 a:R=CH₂CH₃;1 b:R=CH₂CH₂CH₃) are obtained by reaction of sulphamoyl chloride with the appropriate hydroperoxides in the presence of pyridine (temperature below –30 °C, solvent diethyl ether). The solvent-free liquids1 deflagrate at ca. 0 °C. Hydrolysis or ammonolysis of1 generates the hydroperoxide and sulphamic acid or sulphamide, respectively. Controlled thermolysis of1 affords sulphamic acid and carbonyl compounds, i.e. propanal andn-propyl propanoate from1 a, butanal, 2-methylpropanal andn-butyln-butyrate from1 b. These products suggest a nonradical cyclic decomposition path-way.

     

Reaktionen von (−)-Ephedrin bzw. (+)-Norpseudoephedrin und Derivaten mit N,N-Dimethylacetamid-dimethylacetal und N,N,-Dimethylformamid-dimethylacetal

Summary The reactivity of (–)-ephedrine (2) and (+)-norpseudoephedrine (3) towards the amidacetals1 a/b has been studied. Both2 and3 were acetylated resp. formylated at first at the amino group. Nevertheless, derivatives of2 and3 possessing a trisubstituted amino group react with1 a in a [3.3] sigmatopic rearrangement toortho substituted dimethylcarbamoylmethyl derivatives. By subsequent reduction with lithiumaluminiumhydride the aromatic compounds8,13, and18 with two aminoethyl groups are easily available. In contrast to these results1 b did not furnish any rearrangement products.

     

Synthese und Konfigurationszuordnung eines potentiell antimikrobiellen 5,6-Dihydroxyisobenzofuranons

Summary Isobenzofuranone3 was prepared by KMnO₄-oxidation of2. 3 was reacted to give acetals4–10, which adopt the boat-conformation.3 and its acylated derivatives11–13 on the other hand prefer the chair-conformation. The relative configurations of3–13 at the chiral centres 3a, 5, 6, and 7a were determined by¹H-NMR-spectroscopy.

     

Synthese und Reaktionen von 2-Arylhydrazono-2-cyan-N,N-dialkyl-acetamidinen

Summary The title compounds3 were synthesized by reaction of arlyhydrazono-malononitriles1 with secondary amines and used for subsequent cyclization reactions. Thus,3 undergoes cyclooxidation by treatment with CuSO₄/pyridine to form the 5-dialkylamino-2-aryl-1,2,3-triazolo-4-carbonitriles4. From4 a and hydrazine hydrate/DMF the 4-(1,3,4-triazolyl-5)-1,2,3-triazole5 c is obtainable. The chloroacetylation of3 is accompanied by hydrolysis of the amino group to yield the arylhydrazono-N-chloracetyl cyanoacetamides6. The quaternisation of6 with pyridins is followed by the Thorpe cyclization to form the 4-amino-5-arylazo-6-hydroxy-3-pyridinio-pyrid-2-on-chlorides8, useful as cationic dyes. The reaction of3 with trichloroacetonitriles yields the 5-arylazo-4-imino-2-trichlormethyl-1,4-dihydropyrimidines10 a–c which can be converted into the 5-arylazo-2-hydrazino-pyrimidine derivatives10 d–f.From10 d the 6-phenylazo-triazolo[4,3-a]pyrimidine derivative11 is obtainable. From3 and phenylisothiocyanate the 5-arylazo-4-imino-1,4-dihydropyrimidin-2-thiones12 arise. The structures were investigated by¹³C-NMR-spectroscopy.

Herrn Prof. Dr. Fritz Sauter zum 60. Geburtstag gewidmet     

Präparation und Kristallstrukturanalyse von Ca(N3)2(C5H5N)2

Diazido-dipyridine-calcium was prepared by the reaction of Ca(N₃)₂ with pyridine. The crystals are tetragonal, space group I 2 m (121),N=2,a=699.7 (1),c=1 450.6 (5) pm. The crystal structure was determined by single crystal X-ray diffraction, 415 independent observed Mo-K-counter reflexions,R=0.049. The calcium atoms are sixcoordinated to four nitrogen atoms of azide groups and to two nitrogen atoms of pyridine. The coordination polyhedra are tetragonal bipyramids which are linked together by four azide groups to form sheets of composition Ca(N₃)₂. The pyridine rings are directed perpendicular to the sheets.

     

Enantiomere und diastereomere 2-Methoxymethyl-pyrrolidin-1-dithiocarbonsäureester

Summary Formation of the 2-methoxymethyl-pyrrolidine-1-dithiocarboxylates2–4 and alkylation of2 and3 were studied. Enantiomeric and diastereomeric derivatives of4, the preparation of diastereomeric mixtures of4 by alkylation of3 in the presence of strong bases, and formation of6 by phase transfer alkylation of2 are described. The two enantiomers of 2-(4-bromophenyl)-2-oxo-ethyl 2-methoxymethylpyrrolidine-1-dithiocarboxylate2 have been characterized by X-ray analysis.

Verstorben am 22. Juni 1996     

Darstellung und Reaktionen des 2,2,4-Trimethylimidazolin-5-thions

Zusammenfassung 2,2,4-Trimethylimidazolin-5-thion (1) entsteht in guter Ausb. bei der gemeinsamen Einwirkung eines großen Überschusses sowohl an Schwefel als auch an Ammoniak auf Aceton bei Temperaturen von etwa –60° C in Gegenwart bestimmter reaktionsbeschleunigender Zusätze. 1 bildet ein Cu(I)-Salz und läßt sich mit H₂O₂ in alkal. Lösung zum 2,2,4-Trimethylimidazolin-5-on (3) umsetzen.1 reagiert in guten bis sehr guten Ausbeuten mit primären und sekundären Aminen zu 2,2,5-Trimethyl-4-alkylamino-2H-imidazolen (4–12).

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Preparation and reactions of 2.2.4-trimethylimidazoline-5-thion (joint action of sulfur and ammonia upon ketones, LXX. Action of sulfur and ammonia upon acetone, II)

2.2.4-Trimethylimidazoline-5-thione (1) is obtained in good yields by the joint action of a large excess of sulfur and ammonia upon acetone at temperatures around –60° C in presence of certain accelerators. 1 gives a Cu(I)-salt and is converted by alkaline H₂O₂ to 2.2.4-trimethylimidazoline-5-one (3).1 reacts fairly smoothly with primary and secondary amines to yield 2.2.5-trimethyl-4-alkylamino-2H-imidazoles (4–12).

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69. Mitt.:F. Asinger, A. Saus, H. Offermanns undF. Abo Dagga, Ann. Chem.723, 119 (1969).

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1. Mitt.:M. Thiel undF. Asinger, Ann. Chem.610, 17 (1957).

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Teil der DissertationF. Abo Dagga, Techn. Hochschule Aachen 1968.     

Karl Fischer-Reagentien ohne Pyridin(2)

Ohne Zusammenfassung

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Karl Fischer reagents without pyridine(2)Determination of water in cysteine hydrochloride monohydrate

Teil 1: Fresenius Z. Anal. Chem. 303, 203 (1980)     

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.

     

Fungizide Pyridinderivate, 3. Mitt.: Unerwarteter Verlauf nukleophiler Substitutionen an einem Pyridinderivat

Summary In the course of substitution reactions for the synthesis of new types of fungicides, 3-(1-phenyl-1,2,2,2-tetrachloroethyl)-pyridine (2 c) showed an unexpected substitution behaviour: amino substituents were introduced into the pyridine ring and not into the side-chain.

     

Karl-Fischer-Reagentien ohne Pyridin (4)

Zusammenfassung Mit Diethanolamin oder Morpholin können KF-Reagentien hergestellt werden, die genau so stabil sind wie die pyridinhaltigen Reagentien. Für die Wasserbestimmungen sind sie besser geeignet, denn die Titrationen verlaufen rascher.

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Karl Fischer reagents without pyridine (4)One-component reagents

Summary Karl Fischer reagents can be prepared by means of diethanolamine or morpholine instead of pyridine. The new reagents are better suited for water determination because the titration proceeds faster. They are as stable as solutions containing pyridine.

Teil3: Fresenius Z. Anal. Chem. 306, 394–396 (1981)     

Dicyanmethylenpyrazolinone und deren Bedeutung als Chromophor. Synthesen mit Nitrilen, 80. Mitt.

1-Phenyl-2-pyrazolin-5-ones1 a–e react with tetracyanoethylene forming the corresponding dicyanomethylenepyrazolin-5-ones2 a–e. The products are deeply coloured with absorption bands between 550 and 650 nm, but low -values and negative solvatochromic effect. By amine-HCN exchange reaction with anilines the red-coloured phenylamino-cyanomethylene-pyrazolinones3–6 are obtained.¹⁵N- and¹³C-NMR-data of2 and quantum-chemical calculations (INDO/S-CI) reveal the extreme polarization and chromophoric properties of the described dicyanomethylene-pyrazolinones.

     

Untersuchungen über Chinone, 10. Mitt. Zur Reaktion vonp-Benzochinon mit sekundären aliphatischen Aminen

Summary p-Benzoquinone (1) reacts with dialkylamines2a-d to 2-dialkylamino-p-benzoquinones3, 2,5-bis-dialkylamino-p-benzoquinones4, 2-dialkylamino-8-hydroxydibenzofuran-1,4-quinones5, and in pyridine also to 2-dialkylamino-5-p-hydroxy-phenoxy-p-benzoquinones6. A method affording almost exclusively3 has been developed which is also applicable to compounds2e-h.