Über das Verhalten von Betainen gegenüber Phenylisocyanat

Zusammenfassung Pyridinbetain reagiert mit Phenylisocyanat unter Verlust von CO₂ und H₂ zum 2-Oxo-1,3-diphenyl-4-(1-pyridinio)-2,3-dihydro-imidazol-5-olat (1a), während sich Thetin mit dem genannten Reagens zum 2,4-Dioxo-1,3-diphenyl-5-(dimethylsulfonio)-1,2,3,4-tetrahydro-pyrimidin-6-olat (2a) umsetzt.

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Reaction of betaines with phenyl isocyanate (reactions with betaine, III)

(1-Pyridinio)acetate reacts with phenyl isocyanate under the loss of CO₂ and H₂ yielding 2-oxo-1.3-diphenyl-4-(1-pyridinio)-2.3-dihydro-imidazol-5-olate (1a). The reaction of thetine with phenyl isocyanate gives 2.4-dioxo-1.3-diphenyl-5-(dimethylsulfonio)-1.2.3.4-tetrahydro-pyrimidin-6-olate (2a).

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Auszugsweise vorgetragen anläßlich der Chemikertagung in Wien, September 1968.     

2,4-Diaminodihydropyridine

Aminolysis of 4-alkylamino- and 4-dialkylamino-2-methylthiodihydropyridines (· HI)1, 2 resp.. under various reaction-condition leads to assymmetrically or symmetrically substituted 2,4-bisalkylamino- or 2,4-bisdialkylamino-and 2-alkylamino-4-dialkylamino- or 2-dialkylamino-4-alkylaminodihydro-pyridines3, 4, 5, 6 resp. On treatment with alkali only the aminogroup in pos. 4 of the pyridines3, 4, 5, 6 is hydrolyzed and 4-hydroxy-2-aminopyridines9 are formed. Different substituted 2,4-diaminodihydropyridines3, 4, 5, 6 can also be synthesized by reaction of 4-hydroxy-2-aminopyridines (·HCl)9 with amines. Also the aminolysis of 4-alkylamino-annd 4-dialkylaminodihydropyridinthiones7, 8 resp. is described.

     

New syntheses of 2,4-diaminopyrroles and aminopyrrolinones

Summary Oxazolin-2-ylidene-malononitriles3a–d, obtainable from thioketenaminals and -halogen-ketones, react with primary and secondary amines to afford 2,4-diamino-pyrroles5a–h. Mercaptobenzen as nucleophilic agent gives the 4-amino-2-phenylthio-pyrrole5j. Analogously, cyano-(3,5-diphenyl-3H-oxazol-2-ylidene)-acetic acid methyl esters were prepared as intermediates for the synthesis of 2-amino-4-oxo-pyrrolines10a–d. The isomeric 4-amino-2-oxo-pyrrolines13a–d can be obtained from 4-amino-2-methoxy-pyrroles, which serves as proof for the position of substituents. The structures were investigated by¹H and¹³C NMR spectroscopy.

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Neue Synthesen von 2,4-Diaminopyrrolen und Aminopyrrolinonen

Zusammenfassung Die Oxazolin-2-yliden-malononitrile3a–d. die aus Thioketenaminalen und -Halogenketonen erhalten wurden, reagieren mit primären und sekundären Aminen zu den 2,4-Diaminopyrrolen5a–h. Mercaptobenzol als nukleophiles Reagens liefert 4-Amino-2-phenylthiopyrrol (5j). Analog wurden Cyan-(3,5-diphenyl-3H-oxazol-2-yliden)-essigsäuremethylester als Zwischenprodukte für die Synthese der 2-Amino-4-oxo-pyrroline10a–d hergestellt. Die isomeren 4-Amino-2-oxo-pyrroline13a–d können aus den 4-Amino-2-methoxy-pyrrolen11a,b erhalten werden, was als Nachweis für die Position der Substituenten dient. Die Verbindungen wurden¹H- und¹³C NMR-spektroskopisch untersucht.

     

[2+2]-Photocycloaddition von Cyclohexen an 2-Acetyl-5,5-dimethyl-1,3-cyclohexandion und 3-Acetyl-1,5,5-trimethyl-2,4-pyrrolidindion

Summary Irradiation of solutions of excess cyclohexene and 2-acetyl-5,5-dimethyl-1,3-cyclohexanedione (1), and 3-acetyl-1,5,5-trimethyl-2,4-pyrrolidinedione (4) results mainly in the formation of 1,5-diones2 and5. These originate from intermediate cycloadducts of cyclohexene and theexo-enols of the cyclic 1,3-diketones. The yields decrease with increasing polarity of the solvent. In solution2 and5 are in equilibrium with the cyclic hemiacetales3 and6.

     

Diphenyldiaza-18-krone-6-bis-pyrazoliden-acetonitril,ein neuer Chromoionophor Synthesen mit Nitrilen, 90.Mitt.

Summary An improved synthesis of 7,16-diphenyl-1,4,10,13-tetraoxa-7,16-diaza-cyclooctadecan (5) is presented and the reaction with 4-dicyanomethylene-3-methyl-1-phenyl-2-pyrazolin-5-on to the colorless adduct6 described. By heating or photolysis6 can be converted to the deeply colored polymethine7. Complex formation constants with potassium ion by¹H-NMR-measurements have been determined.

Prof. Dr. E. Ziegler zum 80. Geburtstag gewidmet     

Heterocyclic synthesis with 3-cyano-2(1H)pyridinethione: Synthesis of 3-oxo-2,3-dihydroisothiazolo[5,4-b]pyridine and related compounds

Summary 3-Carbethoxy-4,6-diphenyl-2-pyrridine sulfonamide (5), can be cyclized to 3-oxo-2,3-dihydro-4,6-diphenylisothiazolo[5,4-b]pyridine-1,1-dioxide (2). Oxidation of pyridinethione6 with Cl₂/H₂O gave the sulfonyl chloride derivative7, which can be ammonolyzed to 3-amino-4,6-diphenylisothiazolo[5,4-b]pyridine-1,1-dioxide (8), and 3-cyano-4,6-diphenylpyridine-2-sulfonamide (9). Hydrolysis of6 gave 3-carboxamido-2(1H)pyridinethione (12) which can be oxidized with iodine to 3-oxo-4,6-diphenyl-2,3-dihydroisothiazolo[5,4-b]pyridine (13). 3-Methyl-4,6-diphenylisothiazolo[5,4-b]pyridine-1,1-dioxide (17) was also prepared from6.

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Heterocyclensynthese mit 3-Cyano-2(1H)pyridinthion: Synthese von 3-Oxo-2,3-dihydroisothiazolo-[5,4-b]pyridin und verwandten Verbindungen

Zusammenfassung 3-Carbethoxy-4,6-diphenyl-2-pyridinsulfonamid (5) kann zu 3-Oxo-2,3-dihydro-4,6-diphenylisothiazolo[5,4-b]pyridin-1,1-dioxid (2) cyclisiert werden. Die Oxidation des Pyridinthions6 mit Cl₂/H₂O ergab das Sulfonylchlorid-Derivat7, das mit Ammoniak zu 3-Amino-4,6-diphenylisothiazolo[5,4-b]pyridin-1,1-dioxid (8) und 3-Cyano-4,6-diphenylpyridin-2-sulfonamid (9) umgesetzt werden kann. Die Hydrolyse von6 ergab 3-Carboxamido-2(1H)pyridinthion (12), das mit Jod zu 3-Oxo-4,6-diphenyl-2,3-dihydroisothiazolo[5,4-b]pyridin (13) oxidiert wurde. 3-Methyl-4,6-diphenyl-isothiazolo[5,4-b]pyridin-1,1-dioxid (17) wurde ebenfalls aus6 hergestellt.

     

Dithiobiuretes in reactions with electrophilic acetylenes. New derivatives of 1,3,5-dithiazines,-thiadiazines and-triazines as the products of competing reactions of nucleophilic cycloaddition

The nucleophilic addition of 2,4-dithiobiurete, 1- and 1,4-substituted 2,4-dithiobiuretes (2 a-e) with benzoylacetylene (1) has been studied. 2-(Benzoylmethyl)-4-(R¹-imino)-6-(R²-imino)dihydro-4H-1,3,5-dithiazinium perchlorates (3 a-e) are obtained in glacial acetic acid (AcOH) in the presence of equimolar quantities of HClO₄. The reaction of benzoylacetylene with 1,5-diphenyl-2,4-dithiobiurete in either of MeOH, C₆H₆, or MeCN solvents proceeds non-selectively to give a mixture of products such as 2-(benzoylmethyl)-4,6-di(phenylimino)dihydro-4H-1,3,5-dithiazine (5), 2-(benzoylmethyl)-4-(β-benzoylvinyl)thio-3-phenyl-6-(phenylimino)-3,6-dihydro-2H-1,3,5-thiadiazine (8), 2-(benzoylmethyl)-1,3-diphenylhexahydro-1,3,5-triazine-4,6-dithione (7) and N-(β-benzoylvinyl)-N-phenylthioureas (6).     

Darzens reaction as a convenient method for the synthesis of α-chloroketones, α-chloroepoxides,and symmetrically substituted dioxines

Summary TheDarzens reaction of dichloroacetophenone (DCAP) with substituted benzaldehydes has been studied. The structure of the products was shown to depend on the phenyl group substituents. Reaction of benzaldehyde, 4-bromo-, and 2,4-dichlorobenzaldehydes results in 1-phenyl-3-aryl-3-chloropropane-1,2-diones (2a–c), reaction ofpara- ormeta-nitrobenzaldehydes yields 1-phenyl-2-chloro-3-aryl-2,3-epoxypropane-1-ones (3a, b). Upon the introduction of an alkoxy group into the phenyl ring of benzaldexyde and/or dichloroacetophenone, symmetrically substituted dioxines were obtained (6a–c). The structure of the reaction products has been established by single crystal X-ray investigations.

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Darzens-Reaktion als bequemes Verfahren zur Synthese von -Chloroketonen, -Chloroepoxiden und symmetrisch substituierten Dioxinen

Zusammenfassung DieDarzens-Reaction von Dichloracetophenon (DCAP) mit substituierten Benzaldehyden wurde untersucht. Die Struktur der Produkte ist von den Substituenten an der Phenylgruppe abhängig. Die Umsetzung mit Benzaldehyd, 4-Brom- und 2,4-Dichlorbenzaldehyd liefert 1-Phenyl-3-aryl-3-chloropropan-1,2-dione (2a–c), die Reaktion vonpara- odermeta-Nitrobenzaldehyd 1-Phenyl-2-chloro-3-aryl-2,3-epoxipropan-1-one (3a,b). Durch Einführung einer Alkoxygruppe in den Phenylring des Benzaldehyds und/oder des Dichloracetophenons erhält man symmetrisch substituierte Dioxine (6a–c). Die Struktur der Reaktionsprodukte wurde mittels Röntgenstrukturanalyse bestätigt.

     

Azines and Their Acyclic Derivatives as Transferers of One-carbon Fragment in Reactions with Pyrazolones

Enehydrazine derivatives have been obtained by the reaction of 6-phenyl-1,2,4-triazine 4-oxide with pyrazolones 2, which on further heating with pyrazolones 2 are converted into the corresponding symmetrical or unsymmetrical derivatives of dipyrazolylmethane. Enehydrazine derivatives of 1,3-dimethyl-5-nitrosouracil and 1,3-dimethylimidazolidine interact with 3-methyl-1-phenyl-5-pyrazolone (2a) with the formation of dipyrazolylmethane derivative. On interacting compound 2a or 3-methyl-1-(p-nitrophenyl)-5-pyrazolone with 3,6-diphenyl-1,2,4-triazine 4-oxide 12 the corresponding 4,4'-bispyrazolones are formed, but the interaction of compound 12 with 3-(p-nitrophenyl)-1-phenyl-5-pyrazolone leads to dipyrazolylmethane derivative. Dipyrazolylmethane derivative is obtained on heating of fervenulin 4-oxide, 2,4-dihydroxy-5-nitropyrimidine, and 1,3,5-triazines: 6-azauracil, 5-azauracil, azacytosine, and 2,4-diamino-s-triazine with pyrazolone 2a.     

Acylderivate von 2-Amino-p-pyrrolinen

Zusammenfassung Die Acylierung von 2-Amino-3.3-diphenyl-5-methyl-1-pyrrolin (1) und 2-Amino-3.3-diphenyl-1-pyrrolin (2) erfolgt in den hier untersuchten Fällen am N-2-(exo)-Stickstoff. Die Umsetzung der cyclischen Amidine1 und2 mit BrCN gibt jedoch neben den N-2-(exo)-auch die N-1-(endo)-Cyanamidine. Diese werden in die entsprechenden Carbamoyl- und Thiocarbamoylamidine umgewandelt.

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Acylderivatives of 2-amino-1-pyrrolines

Acylations of 2-amino-3.3-diphenyl-5-methyl-1-pyrroline (1) and 2-amino-3.3-diphenyl-1-pyrroline (2) occur at the N-2-(exo)-nitrogen. However, reaction of1 and2 with BrCN yields not only the N-2-(exo)-cyanoamidines but also the N-1-(endo)-isomers. Either is converted into the corresponding carbamoyl and thiocarbamoyl amidines.

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3. Mitt.:W. Klötzer undB. Schmidt, Mh. Chem.102, 180 (1971).

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Teile dieser Arbeit sind Gegenstand von Patentanmeldungen.     

Etherspaltung an Pyridinen mit ungewöhnlichem Halogenierungsverlauf zu isomeren Diamino-pyridon-carbonitrilen und ihre Verwendung als Kupplungskomponenten

Ether cleavage of the two isomeric diamino-methoxy-pyridine-carbonitriles1 and2 leads to the isomeric 4,6-diamino-2(1H)-pyridone-3-carbonitrile (3 a) and 2,4-diamino-6(1H)-pyridone-3-carbonitrile (4 a), resp. Dependent on the reaction conditions in glacial acetic acid containing hydrogen bromide or potassium iodide the halogenated pyridones (3 b, 4 b–c) can be obtained.pK _s -values and UV-spectra of the pyridones are discussed.3 a and4 a can be used as azo-coupling components, yielding the azo-dyes5 and6. Similarly 4-amino-6-hydroxy-2(1H)-pyridones (7 a–b) are coupled with several aryl- and heteroaryl-diazoniumsalts to form the azo-dyes8 a–g.

Herrn emer. o. Univ.-Prof. Dr.Otto Hromatka zum 80. Geburtstag gewidemet.     

Chinazolincarbonsäuren, 10. Mitt. Synthese von 1-Methyl-2,4-dioxo-chinazolin-3-yl-essigsäure, 2,4-Dioxo-chinazolin-1-yl-essigsäuren, 2,4-Dioxo-1,3-chinazolindiessigsäuren und deren Estern

2,4-Dioxo-quinazolin-1-yl-acetic acid esters (2) were prepared by the reaction of either 3,1-benzoxazine-2,4-diones (1) with urea in the melt or in solution or of the substituted anthranilic acid ester4 with potassium cyanate in acid solution. The anthranilamides5 with trichloromethyl chloroformate (diphosgene) gave also2. Alkaline hydrolysis of2 affords the 2,4-dioxo-quinazolin-1-yl-acetic acids (3), which were independently obtained by the sequence5 6 7. 2,4-Dioxo-1,3-quinazolinediacetic acids (11) were synthesized from1 and glycine ester. Reaction of8 with ethyl chloroformate gave9 and treatment of the latter with KOH furnished the potassium salt10, which was converted to11 by acids.Quinazoline-2,4-dione (12) with ethyl bromoacetate yielded13 and with chloroacetonitrile14. 13 was hydrolyzed to11. 14 could not be converted into11.1-Methyl-3,1-benzoxazine-2,4-dione (15) was transformed under similar conditions into 1-methyl-2,4-dioxo-quinazolin-3-yl-acetic acid (16).

     

Syntheses and transformations of novel nitrogen and sulfur containing morphinanedienes

Summary The synthesis of 6-azido-6-demethoxythebaine (10) has been performed starting from thebaine (1). Compound10 undergoes a cycloaddition reaction with the azadienophilePTAD to form bridgehead azide14. The acid catalyzed rearrangement of isothiocyanato diene11 obtained from azido diene10 and thiocyanato dienes8 and9 leads to sulfur containing derivatives of apocodeine (17–20).

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Darstellung und Reaktionen stickstoff- und schwefelhaltiger Morphinandiene

Zusammenfassung 6-Azido-6-demethoxythebain (10) wurde ausgehend von Thebain (1) hergestellt. Verbindung10 wurde in einer Cycloadditionsreaktion mit dem AzadienophilPTAD zum Brückenkopfazid14 umgesetzt. Das aus dem Azidodien10 erhältliche Isothiocyanatodien11 und die bereits früher gewonnenen Thiocyanatodiene8 und9 liefern bei säurekatalysierter Umlagerung die Apokodeinderivate17–20.

     

On the tautomerism of 2,4-disubstituted 3,4,5,6-tetrahydrobenzo[h]quinazolines

Summary The tautomerism of the title compounds was investigated by¹H-,¹³C-NMR and UV spectroscopy. Compound5 was compared with respect to its spectra with those of appropriate model compounds1,3,4, and6. This gave evidence that5 predominates in the tautomeric from5A.

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Zur Tautomerie von 2,4-disubstituierten 3,4,5,6-Tetrahydrobenzo[h]chinazolinen

Zusammenfassung Die Tautomerie von 2,4-disubstituierten 3,4,5,6-Tetrahydrobenzo[h]chinazolinen wurde durch¹H-,¹³C-NMR- und UV-Spektroskopie untersucht. Der Vergleich der Spektren von5 und der Modellverbindungen1,3,4 und6 legt nahe, daß für5 das Tautomere5A dominiert.

     

Synthesen von Heterocyclen, 158. Mitt

Zusammenfassung 4-Benzoyl-5-phenyl-2.3-dihydrofuran-2.3-dion (1) wandelt sich beim Erhitzen auf 120–140° unter Abgabe von CO und CO₂ in 3.5-Dibenzoyl-2.6-diphenyl-4-pyron (2, 79% d. Th.) um. Nimmt man die therm. Zers. in Toluol in Gegenwart katalyt. Mengen Säure vor, so bildet sich 3.7-Dibenzoyl-4.8-diphenyl-1.5-dioxocin-2.6-dion (3, 90% d. Th.). Als gemeinsame Zwischenstufe wird das Dibenzoyl-keten (4) postuliert.

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Syntheses of heterocycles, CLIV (reactions of cyclic oxalyl compounds, V)

4-Benzoyl-5-phenyl-2.3-dihydrofuran-2.3-dione (1) is converted at 120–140° under the loss of CO and CO₂ to yield 3.5-dibenzoyl-2.6-diphenyl-4-pyrone (2, 79%). However, 3.7-dibenzoyl-4.8-diphenyl-1.5-dioxocin-2.6-dione (3) is formed in 90% yield, if1 is decomposed in boiling toluene in the presence of acids. The dibenzoyl ketene4 is postulated as the common intermediate.

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Herrn Prof. Dr.M. Pailer, Univ. Wien, mit freundschaftlichen Grüßen und besten Wünschen zum 60. Geburtstag gewidmet.     

Zur Chemie der 4-Aminothiazolin-2-thione

4-Aminothiazolin-2-one-hydrazones3 are obtained by succesive treatment of the title compound1 with dimethyl sulfate and hydrazinehydrate. The rearrangement of 4-aminothiazolin-2-ylidenmalononitrile7 derived from1 yields the 2,4-diamino-thiophene derivatives8. Analogously, the 4-aminothiazolin-2-yliden-cyanamides10 react to form the substituted 2,4-diaminothiazoles11. Succesive reaction of the ethyl (4-amino-2-thioxo-thiazolinyl-3)-acetates12 with dimethyl sulfate and malononitrile yields the 3,6-diamino-pyrrolo[2,1-b]-thiazoles14.

     

Über die Umsetzung von 2-Methyl-2,5-diphenyl-imidazolin-4-thion und 2-Methyl-2,5-diphenyl-4-chlor-2H-imidazol mit aliphatischen und aromatischen Aminen,Alkoholen und Phenolen

Zusammenfassung Aliphatische Amine bzw. Alkohole reagiren (in Gegenwart von PbO) mit 2-Methyl-2,5-diphenyl-imidazolin-4-thion (1) glatt zu 4-Alkylamino-2H-imidazolen (2 a-f, 7) bzw. 4-Alkoxy-2H-imidazolen (9 a-g). Die Darstellung von 4-Arylamino-2H-imidazolen (4 a-j) bzw. 4-Aroxy-2H-imidazolen (10 a-t) gelingt in guten Ausbeuten durch Umsetzung von 2-Methyl-2,5-diphenyl-4-chlor-2H-imidazol (3) mit aromatischen Aminen in siedenden Lösungsmitteln (Petroläther, Aceton) bzw. mit Phenolen in siedendem Aceton in Gegenwart von HCl-Acceptoren (K₂CO₃, Dabco). Die Umsetzung von3 mit Anthranilsäure liefert in 83proz. Ausbeute 1-Methyl-1,3-diphenyl-1H, 9H-imidazo[5,1-b]chinazolin-9-on (6). Aus3 und Thiophenol erhält man glatt 2-Methyl-2,5-diphenyl-4-phenylthio-2H-imidazol (11).

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On the reaction of 2-Methyl-2,5-diphenyl-imidazoline-4-thione and 2-Methyl-2,5-diphenyl-4-chloro-2H-imidazole with aliphatic and aromatic amines, alcohols and phenols (joint action of elemental sulfur and gaseous ammonia upon ketones, LXXVI

Aliphatic amines and alcohols (in the presence of PbO) easily react with 2-methyl-2.5-diphenyl-imidazoline-4-thione (1) to 4-alkylamino-2H-imidazoles (2 a-f, 7) and 4-alkoxy-2H-imidazoles (9 a-g), resp. 4-arylamino-2H-imidazoles (4 a-j) are prepared in good yields by the reaction of 2-methyl-2.5-diphenyl-4-chloro-2H-imidazole (3) with aromatic amines under reflux in light naphtha or acetone; in the same manner 4-aroxy-2H-imidazoles (10 a-t) are obtained from3 and phenols in boiling acetone in the presence of HCl-acceptors (K₂CO₃, Dabco). Reaction of3 with anthranilic acid leads to1-methyl-1.3-diphenyl-1H.9H-imidazo[5.1-b]chinazoline-9-one (6) in 83% yield. By reaction of thiophenol with3 2-methyl-2.5-diphenyl-4-phenylthio-2H-imidazole (11) is easily obtained.

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Herrn Prof. Dipl.-Ing., Dr. techn., Dr. e. h.Otto Kratky zum 70. Geburtstag herzlichst gewidmet.

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Teil der DiplomarbeitJ. Gräber, Techn. Hochschule Aachen, 1970.

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Teil der DiplomarbeitU. Lames, Techn. Hochschule Aachen, 1971.     

Synthesen von Heterocyclen, 102. Mitt.: Über das Methantricarbonsäure-diäthylesteranilid

Zusammenfassung Dem nachIngold undWeaver ¹ aus Methantricarbonsäurediäthylesteranilid (1) durch Thermolyse darstellbaren Produkt kommt nicht die Struktur des 6-Anilino-3-phenyl-2,4-dioxo-3,4-dihydro-2H-1,3-oxazins (3), sondern die des 2,4-Dioxo-3,3-bis-(carboxyanilino)-1,2,3,4-tetrahydro-chinolins (6) zu.

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The thermolysis of diethyl methanetricarboxylate anilide has been re-examined and found to give mainly 2.4-dioxo-3.3-bis-(carboxanilino)-1.2.3.4-tetrahydro-quinoline (6) and not 6-anilino-3.4-dihydro-3-phenyl-2H-1.3-oxazin-2.4-dion (3) as proposed byIngold andWeaver ¹.

     

Synthesis of some substituted triazolo[4,3-b][1,2,4]triazines as potential anticancer agents

The synthesis of some 3-substituted amino-6,7-diphenyl-1,2,4-triazolo[4,3-b][1,2,4]triazines (15) by cyclodesulfurisation of the corresponding N-(5,6-diphenyl-1,2,4-triazin-3-yl)-N-[substituted thio (carbamoyl)]hydrazines (3) using dicyclohexylcarbodiimid (DCC) and mercuric chloride is described. Moreover, trials to prepare 3-substituted amino-7-hydroxy-6-methyl-1,2,4-triazolo[4,3-b][1,2,4]triazines were not successful.

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Synthese einiger substituierter Triazolo[4,3-b][1,2,4]-triazine als potentielle Antikrebswirkstoffe

Zusammenfassung Es wird die Synthese einiger 3-substituierter Amino-6,7-diphenyl-1,2,4-triazolo[4,3-b][1,2,4]-triazine (15) mittels Cyclodesulfurisierung der entsprechenden N-(5,6-Diphenyl-1,2,4-triazin-3-yl)-N-[subst.thio(carbamoyl)]-hydrazine (3) unter Verwendung von Dicyclohexylcarbodiimid (DDQ) beschrieben. Versuche zur Herstellung von 3-substituierten Amino-7-hydroxy-6-methyl-triazolo[4,3-b][1,2,4]-triazinen schlugen fehl.

     

Prins-Reaktionen mit Arylaldehyden, 5. Mitt.: Zur Umsetzung mit 2-Buten und mit Cyclohexen

By reaction of 2-[(1RS, 2RS)-2-hydroxy-1-methyl-propyl]-2-phenyl-1,3-dithiane (1 a) withcis-2-butene oxide, subsequent reduction and acetalizationc-4,t-5-dimethyl-r-2,c-6-diphenyl-1,3-dioxane (3 a) andt-4,c-5-dimethyl-r-2,c-6-diphenyl-1,3-dioxane (3 b) were synthesized as model compounds. For the same purpose by aldol reaction of cyclohexanone and reduction (1RS, 2SR)-2[(RS)-hydroxy-(4-methoxyphenyl)methyl]cyclohexanol (7 a), (1RS, 2RS)-2[(SR)-hydroxy-(4-methoxyphenyl)methyl]cyclohexanol (8 a), and (1RS, 2RS)-2[(RS)-hydroxy-(4-nitrophenyl)methyl]cyclohexanol (8 b) and by acetalization (2 , 4 , 4 a, 8 a)-2,4-bis(4-methoxyphenyl)hexahydro-4H-1,3-benzodioxin (9 a) and (2 , 4 , 4 a, 8 a)-2,4-bis(4-nitrophenyl)hexahydro-4H-1,3-benzodioxin (10 b) were obtained. FromPrins reactions, starting with 2-butene3 a,c-4,c-5-dimethyl-r-2,c-6-diphenyl-1,3-dioxane (3 c),r-4,t-5-dimethyl-c-6-phenyl-1,3,2-dioxathiane-2,2-dioxide (4), and (2Z, 4E)-1,5-diphenyl-4-methyl-2,4-pentadien-1-on (5), and starting with cyclohexene (E)-3-(4-methoxybenzylidene)cyclohexenyl-4-methoxyphenyl ketone (11) have been isolated in low yields.

4. Mitt.:Griengl, H., Nowak, P., Mh. Chem.109, 11 (1978).