Über die Einwirkung von Ammoniak auf 5-Chlor-2-(N-methyl-jodmethansulfonamido)-benzophenon

Zusammenfassung 5-Chlor-2-(N-methyl-jodmethansulfonamido)-benzophenon (6 b) reagiert mit flüss. NH₃ zu 6-Chlor-4-hydroxy-1-methyl-4-phenyl-3,4-dihydro-1H-2,1-benzothiazin-2,2-dioxid (7), mit NH₃ in absol. Alkohol zu 6-Chlor-4-hydroxy-3-jod-1-methyl-4-phenyl-3,4-dihydro-1H-2,1-benzothiazin-2,2-dioxid (9). Der Mechanismus dieser Reaktionen wird diskutiert.

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The reaction of ammonia with 5-Chloro-2-(N-methyl-iodo-methanesulfonamido)-benzophenone

The reaction of 5-chloro-2-(N-methyl-jodomethanesulfon-amido)-benzophenone (6b) with liquid or absol. alcoholic ammonia leads to 6-chloro-4-hydroxy-1-methyl-4-phenyl-3,4-dihydro-1H-2,1-benzothiazine-2,2-dioxid (7) and 6-chloro-4-hydroxy-3-jodo-1-methyl-4-phenyl-3,4-dihydro-1H-2,1-benzothiazine-2,2-dioxid (9) resp. The mechanism of these reactions is discussed.

     

Methylpyrimidin—Pyridin-Umlagerung von Dihydro-6-methyl-2 (1H)-pyrimidinthionen bzw.-onen

1-Unsubstituted dihydro-6-methyl-2(1H)-pyrimidinethiones undergo an aminolysis in dialkylformamides or methylformamide resp., at higher temperature, and then are rearranged to 4-dialkylaminodihydro-2(1H)-pyridinethiones6 a, b or the 4-methylamino compound6 c. 1-Alkyl- and 1-aryldihydro-6-methyl-2(1H)-pyrimidinethiones1 b, c and tautom, methylenecompounds2b,c resp., react at the same conditions withDMF not only to 4-alkylamino-or 4-arylaminodihydro-2(1H)-pyridinethiones6 c, d but also to 4-dimethylaminodihydro-2(1H)-pyridinethiones6 a. From 3-substituted dihydro-6-methyl-2(1H)-pyrimidinethiones only the 3-aryl compound12 b is converted byDMF to the corresponding dihydro-4-dimethylamino-1-phenyl-2(1H)-pyridinethione14. Also 4-alkylamino- and 4-arylaminodihydro-2(1H)-pyridones18a, b are formed by heating inDMF at 230°C from 1-alkyl- and 1-aryldihydro-2(1H)-pyrimidinones15b, c and of methylene compounds16b, c resp. 2-Methylimino- and 2-phenyliminodihydro-1,3-thiazinethiones19a, b react inDMF viaDimrothrearrangement to the corresponding 1-alkyl- and 1-phenyl-dihydro-2(1H)-pyrimidinethiones1 b, 2 b, 1 c, 2 c and further to 4-alkylamino-and 4-arylaminodihydro-2(1H)-pyridinethiones6 c, d.     

Synthesen von Heterocyclen, 130. Mitt.: Über das Glomerin und das Arborin

Zusammenfassung Es werden einstufige Synthesen desGlomerins (2) [1,2-Dimethyl-4(1H)-chinazolinon] und desArborins (3) [1-Methyl-2-benzyl-4(1H)-chinazolinon] bekanntgegeben.

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Syntheses of heterocycles, CXXX: Glomerine and arborine

A one step synthesis ofglomerine (2) [1.2-dimethyl-4(1H)-quinazolinone] andarborine (3) [1-methyl-2-benzyl-4(1H)-quinazolinone] is described.

     

Acetylenchemie, 14. Mitt.: PTC-Umsetzung von 9(10H)-Acridinon mit 3-Chlor-3-phenyl-1-propin und 3-Brom-1-phenyl-1-propin

Summary Reaction of 9(10H)-acridinone (2) with 3-chloro-3-phenyl-1-propyne under PTC conditions affords 1-methyl-2-phenyl-6H-pyrrolo[3,2,1-de]acridin-6-one (1 b), 10-(2-chloro-1-methyl-2-phenyl-ethenyl)-9(10H)-acridinone (4), 10-(3-phenyl-1-propynyl)-9(10H)-acridinone (7), and 10-(4-methylene-2,3-diphenyl-2-cyclobuteneylidenemethyl)-9(10H)-acridinone (5). The structure of the last compound which crystallizes in the triclinic system with the space group , was confirmed by X-ray diffraction. Under the same conditions 10-(3-phenyl-2-propynyl)-9(10H)-acridinone (3) and 10-(3-phenyl-1-propynyl)-9(10H)-acridinone (6) were obtained from 9(10H)-acridinone (2) and 3-bromo-1-phenyl-1-propyne.

     

Synthese und polarographisches Verhalten von 2H-Isoindol-4,7-dionen

Summary 2-Phenylthio-1,4-benzoquinone (1 a) reacts with azomethine ylide AY-A to give 2-methyl-5-phenylthio-2H-isoindole-4,7-dione (4 f). With 2-(N-methylanilino)-5-methyl-1,4-benzoquinone (1 b), the azomethine ylide AY-B undergoes cycloaddition to yield an inseparable mixture of 5a-methyl-8-(N-methylanilino)-2,3,5,5a,9a,9b-hexahydro-pyrrolo[2,1-a]1H-isoindole-6,9-dione (5 bI) and 9a-methyl-7-(N-methylanilino)-2,3,5,5a,9a,9b-hexahydropyrrolo[2,1-a]1H-isoindole-6,9-dione (5 bII). The structures of5 bI and5 bII were established on basis of two-dimensional-NMR-techniques. The mechanism of the cycloaddition of azomethine ylides to 1,4-quinones was studied on basis of cyclovoltammetric investigations. To determine the electron affinity of the isoindoledione derivatives4 a–f and5 a–b the peak potentials were measured by differential pulse polarography (DPP).

     

Synthesen von Heterocyclen, 133. Mitt.: Zur Chlorierung von 4-Hydroxy-2-pyridonen

Zusammenfassung Die Chlorierung des 5-Äthoxycarbonyl-4-hydroxy-6-methyl-2-pyridons (1) mit SO₂Cl₂ gibt bei unterschiedlichen Reaktionsbedingungen die chlorierten Derivate2,3 bzw.4. Bei der Reaktion des 4-Hydroxy-6-phenyl-2-pyridons (5) mit SO₂Cl₂ erhält man das 3,3,5-Trichlor-pyridin-2,4-dion (6), das mittels Zn/Eisessig zum Dichlorderivat7 reduziert wird. Durch Hydrolyse von6 und Decarboxylierung entsteht das Enaminketon8.

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Syntheses of heterocycles, CXXXIII: Concerning the chlorination of 4-hydroxy-2-pyridones

Chlorination of ethyl 4-hydroxy-6-methyl-2-pyridone-5-carboxylate (1) with SO₂Cl₂ gives, depending on the reaction conditions, the chlorinated derivatives2,3 and4. The reaction of 4-hydroxy-6-phenyl-2-pyridone5 with SO₂Cl₂ yields 3,3,5-trichloro-pyridin-2,4-dione (6), which can be reduced with Zn/AcOH to give 3,5-dichloro-4-hydroxy-2-pyridone (7). Hydrolysis of6 and decarboxylation leads to the enaminoketone8.

     

Zur Synthese der 4-Dialkylamino-5,6-dihydro-2(1H)-pyridinthione sowie entsprechender 4-Alkylamino- bzw. 4-Arylaminoverbindungen

The rearrangement of 1-alkyl- and 1-aryldihydro-6-methyl-2(1H)-pyrimidinethiones (1 a) or-ones (1 b) and of methylene compounds (2a, 2b) resp., to 4-alkylamino- and 4-arylaminodihydro-2(1H)-pyridinethiones (4 a) or-ones (4 b) takes place via the corresponding 3-alkylamino- and 3-aryl-amino-3-butenylisothiocyanates (3 a) or-isocyanates (3 b). Dialkylamino-dihydro-2(1H)-pyridinethiones (10) are formed by heating dihydro-6-methyl-2(1H)-pyrimidinethiones (6 a) and 3,4-dihydro-6-methyl-1,3-thiazin-2-thiones (6 b) with dialkylformamides and by the reaction of secondary amines with tetrahydro-6-hydroxy-6-methyl-1,3-thiazin-2-thiones (5 a), with N,N-dialkyl-N-(3-oxobutyl)-thioureas (7) and 3-oxobutyl isothiocyanates (8). A general method for the preparation of10 is the reaction of dialkylammoniumrhodanides12, N,N-dialkylthioureas13 and dialkylammonium chlorides and KCNS, resp., with 3-alken-2-ones14 and 4-hydroxy-2-alkanones15, resp. Methyl ketones such as acetone, which readily undergo the aldol condensation, behave analogously. The reactions described take place via the intermediate aminoalkenyl isothiocyanates (9).     

Acetylenchemie, 33. Mitt.: Synthese von 2-substituierten Dihydrofuro[2,3-b]chinolinen

Summary The reaction of 3-iodo-4-methoxy-2(1H)-quinolinone (1) and 3-iodo-4,6,8-trimethoxy-2(1H)-quinolinone (2) with 2-methyl-3-butyn-2-ol under modified Heck-conditions gave the 2-substituted derivatives 2-(1-hydroxy-1-methylethyl)-4-methoxyfuro[2,3-b]-quinoline (3) and 2-(1-hydroxy-1-methylethyl-4,6,8-trimethoxyfuro[2,3-b]-quinoline (4). By a subsequent hydrogenation-reaction with a homogeneous catalyst (PtO₂/Rh₂O₃), the furoquinoline-derivatives yielded the dihydrofuro-[2,3-b]quinolines, identified as 2-(1-hydroxy-1-methylethyl-4-methoxy-2,3-dihydrofuro[2,3-b]quinoline (5) (racemic platydesmine) and 2-(1-hydroxy-1-methylethyl)-4,6,8-trimethoxy-2,3-dihydrofuro-[2,3-b]quinoline (6) (racemic precursor of O⁴-methylptelefolonium salt).

     

Ozonolyse von Olefinen,III: Säurekatalysierte Ozonolyse von 3-Hexen-1,6-und 2-Penten-1,5-dicarbonylderivaten

Summary The ozonolysis of mono-unsaturated compounds containing the structural element =CH-CH₂-R [R=COOH, COOCH₃, CH(OCH₃)₂] was investigated. Reductive ozonolysis of (E)-3-hexene-1,6-dioic acid gives methyl 3,3-dimethoxypropanoate (2), whereas ozonolysis of dimethyl (E)-3-hexene-1,6-dioate (1a) and (Z)-1,1,6,6-tetramethoxy-3-hexene (1b) in a methanolic solution of HCl leads to a mixture of2, dimethyl malonate (3 a) and 1,1,3,3-tetramethoxypropane (3 b). The homologuos derivatives, dimethyl glutaconate (4 a) and 1,1,5,5-tetramethoxy-2-pentene (4 b), were ozonized to give mixtures of2, 3, dimethyl oxalate (5), methyl 2,2-dimethoxyacetate (6 a), and 1,1,2,2-tetramethoxyethane (6 b). The ratios of the various reaction products were determined by gas chromatography. In each case the formation of the bifunctional derivatives2 and6 a was favoured.

     

Über Reaktionen von Nitrosophenolen, 2. Mitt.: Reaktion von 1-Nitroso-2-naphthol mit Orein

Zusammenfassung In der vorliegenden Arbeit wurde die Reaktion von 1-Nitroso-2-naphthol mit Orcin in Äther bei Anwesenheit von HNO₃ studiert. Als Reaktionshauptprodukte wurden 11-Methylbenzo[a]-phenoxazon-(9) (1) sowie dessen 12-Oxid (2) isoliert. Der Reaktionsmechanismus und die Konstitution der erhaltenen Substanzen werden diskutiert. Ferner wurden auch 11-Methyl-5-hydroxy-benzo[a]phenoxazon-(9) (6), 11-Methyl-5-äthoxybenzo[a]phenoxazon-(9), 11-Methyl-5-methoxybenzo[a]phenoxazon-(9) (4), 11-Methyl-5-aminobenzo[a]phenoxazon-(9) (7) und 11-Methyl-5-anilinobenzo[a]phenoxazon-(9) (8) dargestellt.

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In this paper the reaction of 1-nitroso-2-naphthol with orcin in an ether medium in presence of HNO₃ is described. As main products 11-methylbenzo[a]phenoxazone-(9) (1) as well as its 12-oxide (2) were isolated. The reaction mechanism is presented. Identity of the reaction products is verified. 11-methyl-5-hydroxybenzo[a]phenoxazone-(9) (5), 11-methyl-5-methoxybenzo[a]phenoxazone-(9) (4), 11-methyl-5-aminobenzo[a]phenoxazone-(9) (7) and 11-methyl-5-anilinobenzo[a]phenoxazone-(9) (8) are prepared.

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Mit 2 Abbildungen     

Cyclisierung von Oligomeren des Malodinitrils mit Amidinen Synthesen mit Nitrilen, 55. Mitt

Condensation of formamidine-acetate with dimeric malononitrile (1 a) leads to 2,4-diamino-3,5-pyridine-dicarbonitrile (3 a), with acetamidine-HCl the methyl derivative3 b is obtained. Reaction of the codimer of malononitrile and methyl cyanoacetate (1 b) with formamidine yields the aminopyridine3 c, while acetamidine and benzamidine, resp. with1 b react to the 1,4-dihydro-4-pyrimidinylidene-methyl-cyanoacetates4 a-b.

     

Umwandlung von Phthalidisochinolinalkaloiden in Benzazepinalkaloide, 1. Mitt.

Zusammenfassung Als Modell für die geplante Umformung von Phthalidisochinolinalkaloiden in natürliche Benzazepinalkaloide (Rhoeadinalkaloide) wird das aus (–)-Narcotin zugängliche Nornarcein2a oder dessen Äthylester2b ² in das Rheadan8b ¹ übergeführt. Ein Rheadan mit dem aromatischen Substitutionsmuster von8b wurde bisher in der Natur noch nicht aufgefunden.

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Conversion of Phthalideisoquinolines into Benzazepine Alkaloids

As a model for the planned conversion of phthalideisoquinoline alkaloids into natural benzazepine alkaloids (rhoeadine type), nornarceine2a or its ethyl ester2b [obtained from (–)-narcotine,1]² have been transformed into the rheadane8b ¹. The aromatic substitution pattern of8b has not yet been observed in nature.

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Herrn Prof. Dr.O. Kratky zum 70. Geburtstag gewidmet.     

Zur Einwirkung von Schwefel und Aminen auf Dihydro-2(1H)-pyrimidinone bzw.-thione

Zusammenfassung Dihydro-4,4,6-trimethyl-2(1H)-pyrimidinone (1) bzw.-thione reagieren mit Schwefel und Morpholin zu Tetrahydro-2-oxobzw.-2-thiono-4,4-dimethylpyrimidin-6-thiocarbonsäuremorpholiden (3); mit Schwefel in Dimethylformamid bzw. Tetramethylharnstoff bilden sich Dihydro-3-thiono-3H-1,2-dithiolo-[4,3—d]pyrimidin-5(4H)-one (5) bzw.-3,5-dithione. Das Dihydro-6-methyl-4-phenyl-2(1H)-pyrimidinon2 bzw.-thion geben mit Schwefel und Tetramethylharnstoff das Dihydro-1-methyl-2-oxo-bzw.-2-thiono-4-phenylpyrimidin-6-trimethylcarboxamidin (7). Methylheterocyclen, wie Chinaldin, werden bei analoger Behandlung in Chinolin-2-thiocarbonsäuredimethylamid usw. übergeführt.

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Reaction of sulfur + amines with dihydro-2 (1H)pyrimidinones and-thiones

Dihydro-4,4,6-trimethyl-2(1H)-pyrimidinones (1) and-thiones react with sulfur and morpholine to tetrahydro-2-oxo- and-2-thiono-4,4-dimethylpyrimidine-6-thiocarboxylic acid morpholides (3); with sulfur inDMF or tetramethylurea (TMU) the formation of dihydro-3-thiono-3H-1,2-dithiolo[4,3—d]pyrimidin-5(4H)-ones (5) or-3,5-dithiones, resp. was observed. Dihydro-6-methyl-4-phenyl-2(1H)-pyrimidinone (2) (-thione) with sulfur andTMU yields dihydro-1-methyl-2-oxo- and-2-thiono-4-phenylpyrimidin-6-trimethyl-carboxamidine (7). Methyl substituted heterocycles e.g. quinaldine, are converted under analogous conditions to quinoline-2-thiocarboxylic acid dimethylamide and corresponding compounds. *** DIRECT SUPPORT *** A3615139 00018

     

Untersuchungen von Reaktionsmechanismen durch Isotopenmarkierung,VII. Zum Mechanismus der Ringverengung von 2,2-Dichlor-6-methyl-4H-1-thiochroman-3,4-dion

It is shown by use of¹⁴C-labeling that the ring contraction reaction of 2,2-dichloro-6-methyl-4H-1-thiochroman-3,4-dione (1) leads to elimination of C-2 as CO₂. Formation of the 5-methyl-2,3-dihydrobenzo[b]thiophen-2,3-dione (2) is suggested to proceed via hydrolytic opening of the thiolactone-binding in1. recyclisation and subsequent oxidation by unreacted1.

Herrn emer. Univ. Prof. Dr.E. Ziegler zur Vollendung seines 70. Lebensjahres mit besten Wünschen gewidmet.     

Herstellung von 6,14-Ethenomorphinan-Derivaten

Zusammenfassung Dihydronorthevinon (2b) wurde aus Dihydrothevinon (2a) mit Azodicarbonsäurediethylester (DEAD) hergestellt und zu einigen neuen N-substituierten Dihydronorthevinon-Derivaten (2c–2g) umgesetzt. Es wurdenGrignard-Reaktionen dieser Verbindungen mit Methylmagnesiumiodid bzw.tert-Butylmagnesiumchlorid durchgeführt. O-Demethylierungen von3a–3j ergaben die entsprechenden N-substituierten Buprenorphin- bzw. Diprenorphin-Analoga4a–4j.

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Preparation of 6,14-ethenomorphinan derivatives

Summary Dihydronorthevinone (2b) was prepared from dihydrothevinone (2a) with diethyl azodicarboxylate (DEAD) and transformed into a number of new N-substituted dihydronorthevinone derivatives (2c–2g).Grignard reactions of the new compounds with methylmagnesium iodide andtert-butyl-magnesium chloride were studied. O-Demethylation of3a–3j resulted in the corresponding N-substituted buprenorphine and diprenorphine analogs4a–4j.

     

Zum Mechanismus der Reduktion von 1,3-Benzodithiol-2-thionen

Carbophilic reaction of 1,3-benzodithiole-2-thione (1) with trideuteroborane · dimethylsulfide, synthesized from NaBD₄ and BF₃ ·Me ₂S inTHF, gave 2,2-dideutero-1,3-benzodithiole (5 b) as well as the minor side-products7 b,8 and9 b.

     

Synthese von indenothiophenen, 2. Mitt.

The synthesis of 5,6-dihydro-4H-indeno[5,4–b]thiophene (2 b) is described.     

Synthesen von Heterocyclen, 81. Mitt.: Über substituierte Glyoxalhydrazone

Zusammenfassung 3-Phenylazo-4-hydroxy-2-oxo-indeno[1,2-b]pyran (4) läßt sich durch Erhitzen mit verd. Lauge zum 3-Hydroxyindenyl-(2)-glyoxal-2-phenylhydrazon (11) hydrolysieren, welches mit Phenylhydrazin unter Ringschluß zum 1,4-Dihydro-1-phenylindeno-[1,2-c]pyrazol-(3)-aldehydphenylhydrazon (21) reagiert.

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3-Phenylazo-4-hydroxy-2-oxo-indeno[1,2-b]pyran (4) is hydrolysed by heating in aqueous sodium hydroxide solution to 3-hydroxyindenyl-(2)-glyoxal-2-phenylhydrazone (11). This compound reacts with phenylhydrazine under ring closure to 1,4-dihydro-1-phenylindeno[1,2-c]pyrazol-(3)-aldehyde phenylhydrazone (21).

     

Synthesen und Reaktionen von Pyridazinderivaten, 2. Mitt.: 4-Hydroxymethyl-pyridazin

While reduction of ethylpyridazine-4-carboxylate (1 b) by LiAlH₄ or NaBH₄ yields mixtures of 4-hydroxymethyl-pyridazine (1 a) and ethyl-2.5-dihydro-pyridazine-4-carboxylate (2), pyridazine-4-carbaldehyde and 4-acetyl-pyridazine quantitatively by NaBH₄ are reduced to the corresponding carbinols1 a, 1 d. 4-Chloromethyl-pyridazine easily can be prepared by reaction of1 a with SOCl₂. The structures of the new compounds are proved by¹H-NMR-, IR- and mass-spectroscopy.

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1. Mitt.:G. Heinisch, Mh. Chem.104, 953 (1973).     

Methanolyse von 14-Brom-codeinondimethylacetal

Zusammenfassung Bei der Reaktion von 14-Brom-codeinondimethylacetal (1) mit Methanol in Gegenwart von wasserfr. Na₂CO₃ wurden 7-Methoxy-neopinondimethylacetal (2 b) und 14-Methoxy-codeinondimethylacetal (6 b) erhalten. Die Strukturen der neuen Verbindungen werden bewiesen.

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Methanolysis of 14-bromocodeinone dimethyl acetal

Reaction of 14-bromo-codeinone dimethyl acetal (1) with methanol in presence of Na₂CO₃ yields 7-methoxy-neopinonedimethyl acetal (2 b) and 14-methoxy-codeinone dimethyl acetal (6 b). The structures of the new compounds are proved.

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Herrn Prof. Dr.F. Kuffner zum 65. Geburtstag gewidmet.

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Teilergebnisse stammen aus der ZusammenarbeitF. Vieböck undV. Klintz. DissertationV. Klintz, Univ. Wien 1945.