Acetylenchemie 12. Mitt.: Weitere studien über die phasentransfer-katalysierte umsetzung des 9(10H)-acridinons mil alkinylhalogeniden

By the phase transfer catalyzed reaction of 9(10H)-acridinone with 1-bromo-2-propyne, 10-(2-propynyl)-9(10H)-acridinone is synthesized. As prototropic rearrangement products of this 10-(1,2-propadienyl)-9(10H)-acridinone and 10-(1-propynyl)-9(10H)-acridinone are obtained, Under the given conditins 1-bromo-2butyne leads to 10-(2-butynyl)-9(10H)-acridinone and 2-chloro-3-butyne leads to 10-(1-methyl-1,2-propddienyl)-9(10H)-acridinone, 10-(1-methyl-2-propynyl)-9(10H)-acridinone, 9-(1-methyl-2-propynyloxy)acridine and 10-[1-methyl-3-(3,4-dimethylphenyl-2-propynyl)]-9(10H)-acridinone. The formation of the products is experimentally confirmed and with published work compared.     

Natural product chemistry,part 137: Oxidation of acridone alkaloids: Synthesis of 5-methoxyacronycine

Summary Epoxidation of the acridone alkaloid acronycine (1) resulted in hydroxylation at the aromatic ring giving 5-hydroxyacronycine (3). The same reaction on 1,3-dimethoxy-10-methyl-9(10H)-acridinone (5) gave 1,3-dimethoxy-2-hydroxy-10-methyl-9(10H)-acridinone (6), 1,3-dimethoxy-2-hydroxy-4-peroxy-10-methyl-9(10H)-acridinone (8), and 1,3-dimethoxy-2,4-diperoxy-10-methyl-9(10H)-acridinone (9).

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Naturstoffchemie, 137. Mitt.: Oxidierung von Acridonalkaloiden: Synthese des 5-Methoxyacronycins (Kurze Mitt.)

Zusammenfassung Die Epoxidierung des Acridonalkaloids Acronycin führte zu einer Hydroxylierung des aromatischen Rings, wobei 5-Hydroxyacronycin (3) entstand. Die gleiche Reaktion mit 1,3-Dimethoxy-10-methyl-9(10H)acridinon (5) ergab 1,3-Dimethoxy-2-hydroxy-10-methyl-9(10H)acridinon (6), 1,3-Dimethoxy-2-hydroxy-4-peroxy-10-methyl-9(10H)acridinon (8) und 1,3-Dimethoxy-2,4-diperoxy-10-methyl-9(10H)acridinon (9).

     

Acetylenchemie 2. Mitt.: Sigmatrope Umlagerungen bei der phasentransferkatalysierten Umsetzung von 9(10H)-Acridinon mit 3-Chlor-3-methylbut-1-in

1-Isopropyl-pyrrolo[3,2,1-d,e]acridine-6-one and 10-(3,3-dimethylallenyl)-9(10H)-acridinone were obtained by the reaction of 9(10H)-acridinone with 3-chloro-3-methylbut-1-yne under ptc-conditions.

     

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.

     

A study of the Claisen rearrangement of 7-(3-phenyl-2-propenyloxy)-3-phenyl-(4H)-1-benzopyran-4-one derivatives

Summary The Claisen rearrangement of 7-(3-phenyl-2-propenyloxy)-3-phenyl-(4H)-1-benzopyran-4-one (2 a) gave 7-hydroxy-8-(1-phenyl-2-propenyl)-3-phenyl-(4H)-1-benzopyran-4-one (3 a) and 2,3-dihydro-2,6-diphenyl-3-methyl-(7H)furo[2,3-h]-1-benzopyran-7-one (7 a). 2-Methyl-7-(3-phenyl-2-propenyloxy)-3-phenyl-(4H)-1-benzopyran-4-one (2 b) afforded4 b and7 b. 8-Methyl-7-(3-phenyl-2-propenyloxy)-3-phenyl-(4H)-1-benzopyran-4-one (12) gave only the alkali soluble product 7-hydroxy-8-methyl-6-(1-phenyl-2-propenyl)-3-phenyl-(4H)-1-benzopyran-4-one (13).3 a,4 b, and13 were further cyclized in acidic medium to9 a,10 b, and14 followed by dehydrogenation.This paper is dedicated to Dr. F. M. Dean, Department of Organic Chemistry, Robert Robinson Laboratories, University of Liverpool, Liverpool, U. K., on his retirement     

Natural product chemistry. Part 159. Two methods for the synthesis of 4-azaacronycine as a potential antitumor agent

Two different methods for the synthesis of 4-azaacronycine ( 10 ) have been described. One route with a fusion reaction between 1,3-dihydroxy-10-methyl-9(10H)-acridinone ( 1 ) and 2-amino-2-methyl-3-butyne in a glass ampoule and the other by a reaction of 3-amino-1-methoxy-10-methyl-9(10H)-acridinone ( 9 ) with 2-chloro-2-methyl-3-butyne.     

Natural product chemistry. Part 153 . Synthesis and possible anticancer activity of 8-nitronoracronycine

Since the strategy for the synthesis of 9-, 10- and 11-nitronoracronycine [3,4] could not be applied to the 8-nitronoracronycine 9 , we here report the preparation of the latter by a fusion of methyl 2-amino-6-nitrobenzoate 2 and phloroglucinol 3 . The fusion of 2 and 3 gave 1,3-dihydroxy-8-nitro-9(10H)-acridinone 6 . Subsequent methylation, demethylation and reaction with 2-chloro-2-methyl-3-butyne afforded the desired 8-nitronoracronycine 9 . Compound 9 , 1,3-dimethoxy-10-methyl-8-nitro-9(10H)-acridinone 7 and 1,3-dihydroxy-10-methyl-8-nitro-9(10H)-acridinone 8 were tested by the National Cancer Institute (NCI) for possible anticancer activity.     

Über Dihydro-6-methyl- bzw.-6-styryl-4-phenyl-2(1H)-pyrimidinone (-thione) sowie Hexahydro-5-benzoyl- bzw.-cinnamoyl-4,7-diphenyl-2(1H)-chinazolinone (-thione)

Zusammenfassung Dihydro-6-methyl-4-phenyl-2 (1H)-pyrimidinone (-thione) (1) reagieren als -Methylalkenylharnstoffe bzw.-thioharnstoffe mit Säuren zu Hexahydro-4,4-methylendi-2(1H)-pyrimidinonen (-thionen) (3), mit Phenolen zu Tetrahydro-6-hydroxyphenyl-2(1H)-pyrimidinonen (-thionen) (2), mit Benzaldehyd zu 6-Styrylverbindungen (1 d, e, g) und mit ,-ungesättigten Ketonen zu Tetrahydro-2(1H)-chinazolinonen (7). Aus 1,5-Diphenyl-1,4-pentadien-3-on und Harnstoffen, Thioharnstoffen bzw. Ammonrhodanid entstehen Diphenyl-1,3,7,9-tetraazaspiro-5,5-undecan-2,8-dione (9) bzw. Hexahydrotriphenyl-6-cinnamoyl-2(1H)-chinazolinthione (10). Hexahydro-6-benzoyl-bzw.-6-cinnamoyl-2(1H)-chinazolinone (-thione) (10) bilden sich allgemein bei Einwirkung von ,-ungesättigten Ketonen auf Dihydro-4-phenyl-6-styryl-2(1H)-pyrimidinone (-thione) (1 d, e, g).

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Heterocycles, XXVII: Dihydro-6-methyl-(or-6-styryl-)-4-phenyl-2(1H)-pyrimidinones (-thiones); Hexahydro-5-benzoyl-(or-cinnamoyl-)-4,7-diphenyl-2(1H)-quinazolinones (-thiones)

Dihydro-6-methyl-4-phenyl-2(1H)-pyrimidinones (-thiones) (1) react as -methylalkenylureas (-thioureas) with acids to hexahydro-4.4-methylenedi-2(1H)-pyrimidinones (-thiones) (3), with phenols to tetrahydro-6-hydroxyphenyl-2(1H)-pyrimidinones (-thiones) (2), with benzaldehyde to 6-styryl compounds (1 d, e, g) and with ,-unsaturated ketones to tetrahydro-2(1H)-quinazolinones (7).On reacting 1.5-diphenyl-1.4-pentadien-3-one with ureas, thioureas or ammonium thiocyanate, the products formed are diphenyl-1.3.7.9-tetraazaspiro-5.5-undecane-2.8-diones (9) and hexahydrotriphenyl-6-cinnamoyl-2(1H)-quinazolinethiones (10), resp. Hexahydro-6-benzoyl- (or-6-cinnamoyl-)-2(1H)-quinazolinones (-thiones) (10) are formed generally by the action of ,-unsaturated ketones on dihydro-4-phenyl-6-styryl-2(1H)-pyrimidinones (-thiones) (1 d, e, g).

     

Synthesis of 2-acetyl-3-methyl-4H-1,4-benzothiazine and its derivatives

Summary 2-Aminothiophenol (1) reacts with 3-chloro-2,4-pentanedione (2) in the presence of pyridine to form 2-acetyl-3-methyl-4H-1,4-benzothiazine (3) in high yields. Reaction of3 with hydrazine gives 4-(2-aminophenylthio)-3,5-dimethylpyrazole (5). Condensation of3 with 4-nitrobenzaldehyde yields the corresponding Schiff base7. Hydroxylamine with benzothiazine3 affords 3,9a-dimethyl-3a, 9a-dihydro-9H-isoxazolo[4,5-b][1,4]benzothiazine (8).

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Synthese von 2-Acetyl-3-methyl-4H-1, 4-benzothiazin und seinen Derivaten

Zusammenfassung 2-Aminothiophenol (1) reagiert mit 3-Chlor-2,4-pentandion (2) in Anwesenheit von Pyridin unter Bildung von 2-Acetyl-3-methyl-4H-1,4-benzothiazin (3) in sehr hoher Ausbeute. Benzothiazin3 kondensiert mit Hydrazin zu 4-(2-Aminophenylthio)-3,5-dimethylpyrazol (5), dessen Aminogruppe reagiert mit 4-Nitrobenzaldehyd zu einer Schiffschen Base (7), die spektroskopisch charakterisiert wurde. Benzothiazin3 mit Hydroxylamin ergibt 3,9a-Dimethyl-3a,9a-dihydro-9H-isoxazolo[4,5-b][1,4]benzothiazin (8). Die Stereochemie der letztgenannten Verbindung wurde ermittelt.

     

Über die Synthese des 8-Chlor-1-methyl-6-phenyl-1H,3H-4,2,1,5-benzoxathiadiazocin-2,2-dioxids

Heating the Na-salt of 5-chloro-2-(N-methyl-jodomethanesulfonamido)-benzophenone-α-oxime (8) in dimethylformamide yields 8-chloro-1-methyl-6-phenyl-1H,3H-4,2,1,5-benzoxathiadiazocine-2,2-dioxide (9).     

New 1H-1-alkyl-6-methyl-3-phenyl-7-phenylazo-pyrazolo[5,1-c][1,2,4]triazoles through regioselective alkylation of 1H-6-methyl-3-phenyl-7-phenylazopyrazolo[5,1-c][1,2,4]triazoles

1H-1-Alkyl-6-methyl-3-phenyl-7-phenylazopyrazolo[5,1-c][1,2,4]triazoles (2aa-ad) were obtained by regioselective alkylation of 1H-6-methyl-3-phenyl-7-phenylazopyrazolo[5,1-c][1,2,4]triazoles (2a). 1H-1-Alkyl-6-methyl-3-phenyl-7-phenylazopyrazolo[5,1-c][1,2,4]triazoles 2aa and 2ab were also prepared by coupling phenyldiazonium chloride with 1H-1-alkyl-6-methyl-3-phenyl-pyrazolo[5,1-c][1,2,4]triazoles 1aa and 1ab. The new compounds were characterized by IR, UV-VIS, ¹H-NMR, ¹³C-NMR, and ¹⁵N-NMR spectroscopy and their structures and actual tautomeric forms were established unequivocally.      

Über die Umsetzung von 6-Chlor-4-phenyl-3,4-dihydro-1H-2,1,3-benzothiadiazin-2,2-dioxid mit 1,4-Dijodbutan

Zusammenfassung Bei der Umsetzung des Dinatriumsalzes von 6-Chlor-4-phenyl-3,4-dihydro-1H-2,1,3-benzothiadiazin-2,2-dioxid (1) mit 1,4-Dijodbutan inDMF wurde das erwartete 1,3-Butano-derivat nich erhalten.1 wurde einerseits zu 6-Chlor-4-phenyl-1H-2,1,3-benzothiadiazin-2,2-dioxid (4) dehydriert, andrerseits traten je nach Herstellungsweise des Dinatriumsalzes Methylierungsreaktionen ein bzw. es entstanden 6-Chlor-1-(4-jodbutyl)-4-phenyl-3,4-dihydro-1H-2,1,3-benzothiadiazin-2,2-dioxid (7) und 6,6-Dichlor-4,4-diphenyl-3,3,4,4-tetrahydro-3,3-tetramethylenbis(1H-2,1,3-benzothiadiazin)-2,2,2,2-tetroxid (8).

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Reaction of 6-chloro-4-phenyl-3,4-dihydro-1H-2,1,3-benzothiadiazine-2,2-dioxide with 1,4-Diiodobutane. (Cyclic and bicyclic sulfamides III)

On reaction of the disodium salt of 6-chloro-4-phenyl-3,4-dihydro-1H-2,1,3-benzothiadiazine-2,2-dioxide (1) with 1,4-diiodobutane inDMF the expected 1,3-butano derivative was not obtained. On the one hand1 was dehydrogenated to give 6-chloro-4-phenyl-1H-2,1,3-benzothiadiazine-2,2-dioxide (4), on the other hand according to the method of preparation of the disodium salt either methylation reactions occured or 6-chloro-1-(4-iodobutyl)-4-phenyl-3,4-dihydro-1H-2,1,3-benzothiadiazine-2,2-dioxide (7) and 6,6-dichloro-4,4-diphenyl-3,3,4,4-tetrahydro-3,3-tetramethylenebis(1H-2,1,3-benzothiadiazine)-2,2,2,2-tetroxide (8) were formed.

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Herrn Prof. Dr.H. Nowotny gewidmet.     

Transformations of 5-methyl-2-phenyl-2,4-dihydro-3H-pyrazol-3-one under various conditions of cyclopropyldiazonium generation

Cyclopropyldiazonium generated by basic decomposition of N-cyclopropyl-N-nitrosourea easily entered into an azo coupling reaction with 5-methyl-2-phenyl-2,4-dihydro-3H-pyrazol-3-one (2) to give the corresponding cyclopropylhydrazone in up to 90% yield. Competitive processes occurring under the conditions of cyclopropyldiazonium generation by nitrosation of cyclopropylamine with butyl nitrite mainly include nitrosation of the starting pyrazolone 2. Subsequent transformations of the resulting heterocyclic 3-methyl-1-phenyl-1H-pyrazole-4,5-dione 4-oxime yield 4-[cyclopropyl(oxido)imino]-5-methyl-2-phenyl-2,4-dihydro-3H-pyrazol-3-one. Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 12, pp. 2151–2155, December, 2006.     

Potential psychotropic agents. 7-Chloro-9-phenyl-3,3-diethyl-3H-pyrazolo-[5, 1-b]quinazolin-10-ium-2-olate and 9-Chloro-2,3,4,5-tetrahydro-1-methyl-3,3-diethyl-7-phenyl-1H-benzo-1,5,6-triazonine-2,4-dione

2-Amino-5-chloro-α-phenylbenzylidene hydrazone ( 1 ) or its methyl derivative 2 or acetyl derivative 10 react with diethylmalonic esters to give the corresponding malonyl derivatives 3, 4 and 8 . These esters were hydrolyzed to the acids 5 and 6 . Treating 5 with dehydrating agents the mesoionic compound 7-chloro-9-phenyl-3,3-diethyl-3H-pyrazolo[5,1-b]quinazolin-10-ium-2-olate (14) was obtained, while the methyl derivative 6 afforded the desired 9-chloro-2,3,4,5-tetrahydro-1-methyl-3,3-diethyl-7-phenyl-1H-benzo-1,5,6-triazonine-2,4-dione ( 17 ). Some derivatives of these compounds were also described. The structures of the new compounds were confirmed by an alternative synthesis and by mass and prnr spectral data.     

Conversion of 6-phenylimino-2H-thiopyran-4-amines to 1-phenyl-2,3-dihydro-4(1H)-pyridinones

Summary 6-Phenylimino-3,6-dihydro-2H-thiopyran-4-amines (1) were converted to 1-phenyl-5,6-dihydropyridine-2(1H)-thiones (3). Those were akylated and hydrolyzed, thus yielding 6-methylthio-1-phenyl-2,3-dihydro-4(1H)-pyridinones (5). Finally, the methylthio group was removed withRaney nickel giving the title compounds6. The relative configurations of the formed diastereoisomeric dihydropyridinones have been investigated by NOE measurements.

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Umwandlung von 6-Phenylimino-2H-thiopyran-4-aminen zu 1-Phenyl-2,3-dihydro-4(1H)-pyridinonen

Zusammenfassung 6-Phenylimino-3,6-dihydro-2H-thiopyran-4-amine (1) wurden in 1-Phenyl-5,6-dihydropyridin-2(1H)-thione (3) umgewandelt. Diese wurden alkyliert und zu 6-Methylthio-1-phenyl-2,3-dihydro-4(1H)-pyridinonen (5) hydrolysiert. Zuletzt gelangte man durch selektives Entfernen der Methylthiogruppe mitRaney-Nickel zu den Titelverbindungen6. Die relativen Konfigurationen der gebildeten diastereomeren Dihydropyridinone wurden durch NOE-Messungen aufgeklärt.

     

Condensed thiazoles,I: Synthesis of 5,7-disubstituted thiazolo[4,5-d]pyrimidines as possible anti-HIV,anticancer, and antimicrobial agents

Summary A convenient and simple synthesis of 5-mercapto-3-phenyl-2-thioxo-2,3-dihydrothiazolo-[4,5-d]pyrimidin-7(6H-one(2) and its 5,7-dichloro (3), 5,7-diazido (4), 5,7-diamino (5), 5,7-dimerapto (6), 5,7-dimethylthio (7), and 6-methyl-5-methylthio (8) derivatives is described. The prepared compounds were screened for theirin vitro anti-HIV, anticancer, antibacterial and antifungal activities.

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Kondensierte Thiazole, 1. Mitt.: Synthese von 5,7-disubstituierten Thiazolo[4,5-d]pyrimidinen als potentielle anti-HIV, anticancerogene und antimikrobielle Verbindungen

Zusammenfassung Die Synthese von 5-Mercapto-3-phenyl-2-thioxo-2,3-dihydrothiazolo[4,5-d-pyrimidin-7(6H)-on (2) und seiner 5,7-dichloro-(3), 5,7-diazido-(4), 5,7-dimanio-(5), 5,7-dimercapto-(6), 5,7-dimethylthio- (7) und 6-methyl-5-methylthio-Derivaten (8) wird beschrieben. Die hergestellten Verbindungen wurden auf ihrein vitro anti-HIV, anticancerogenen, antibakteriellen und antimykotischen Aktivitäten geprüft.

     

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).     

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.

     

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

     

Formation of fluorene and anthracene derivatives in reactions of perfluorinated 1-alkyl-1-phenyl- and 1-alkyl-2-phenyl-1,2-dihydrocylobutabenzenes with antimony pentafluoride

The reaction of perfluoro(1-methyl-1-phenyl-1,2-dihydrocyclobutabenzene) with SbF₅ at 50°C, followed by hydrolysis, gave perfluoro(1-phenylindan-1-ol), while analogous reaction at 90°C afforded perfluoro[10-methylanthracen-9(10H)-one]. Perfluoro(1-methyl-2-phenyl-1,2-dihydrocyclobutabenzene) did not undergo skeletal transformations under analogous conditions, whereas at 200°C it was converted mainly into perfluoro(9-methylfluoren-9-ol). Perfluoro(1-ethyl-2-phenyl-1,2-dihydrocyclobutabenzene) reacted with SbF5 at 200°C to form perfluoro(9-ethylfluoren-9-ol) together with perfluorinated 9,9-dimethyl- and 9-ethyl-9-methyl-1,2,3,4-tetrahydro-9H-fluorenes.