Phenanthro-imidazole

Zusammenfassung Es wird die Synthese verschiedener Chlor-, Brom- und Nitro-1H-Phenanthro[9,10-d]imidazole beschrieben.

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The synthesis of several chloro-, bromo-, and nitro-1H-Phenathro[9,10-d]imidazoles is described.

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Herrn Professor Dr.F. Wessely zum 70. Geburtstag in Verehrung gewidmet.     

Über Heterocyclen, 17. Mitt.

Zusammenfassung Hexahydro-8a-methylpyrimido[4,5-d]pyrimidin-2,7 (1H, 3H)-dione reagieren mit o-reaktiven Phenolen zu Hexahydro-10a-methyl-2H[1]benzopyrano[2,3-d]pyrimidin-2-onen.

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Heterocycles, XVII: Hexahydro-8a-methylpyrimido[4,5-d]-pyrimidine-2,7 (1H, 3H)-diones

Hexahydro-10a-methyl-2H[1]benzopyrano[2,3-d]pyrimidin-2-ones have been synthesized by the reaction of hexahydro-8a-methylpyrimido[4.5-d]pyrimidine-2.7(1H, 3H)-diones with phenols having reactive o-positions.

     

Synthese von 4H-Pyrano[2,3-d]pyrimidinen

Summary Good yields of substituted 5-(5R-2-furyl)-4H-pyrano[2,3-d]pyrimidines4 were obtained in the reaction of 2-ethoxymethyleneamino-3-cyano-4H-pyranes2 with ammonia. Compounds2 were prepared by the condensation of the starting 2-amino-5-acetyl-3-cyano-6-methyl-4H-pyranes1 with ethyl orthoformate. Spectral properties of the bicyclic system4 in relation to compounds3 are discussed.

     

Concerning the reaction of 2-(10-diazo-10H-anthracen-9-ylidene)-malonodinitrile and related compounds with the cryptohydride system formic acid-triethylamine

Summary The reaction of 2-(10-diazo-10H-anthracen-9-ylidene)-malonodinitrile (1) with the cryptohydride system formic acid - triethylamine was studied. The reaction product turned out to be anthracen-9-yl-acetonitrile (2a) instead of the expected 10-dicyanomethyl-9,10-dihydro-anthracene-9-yl formate. Compounds related to1 yielded in this reaction the corresponding 10-substituted anthracen-9-yl-acetonitriles. A mechanism of this reaction is proposed. The product of the formic acid promoted decomposition of1, compound3b, as well as its tautomer4b were also obtained.

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Zur Reaktion von 2-(10-Diazo-10H-anthracen-9-yliden)-malodinitril und Verwandten Verbindungen mit dem Kryptohydridsystem Ameisensäure - Triethylamin

Zusammenfassung Die Reaktion von 2-(10-Diazo-10H-anthracen-9-yliden)-malodinitril (1) mit dem Kryptohydridsystem Ameisensäure — Triethylamin wurde untersucht. Das Umsetzungsprodukt stellte sich als Anthracen-9-yl-acetonitril (2a) und nicht als erwartetes 10-Dicyanomethyl-9,10-dihydroanthracen-9-yl-format heraus. Verwandte Verbindungen reagierten in dieser Reaktion zu 10-substituierten Anthracen-9-yl-acetonitrilen. Ein Mechanismus für diese Reaktion wird vorschlagen. Das Produkt der durch Ameisensäure initiierten Zersetzung von1, Verbindung3b, wie auch sein Tautomer4b, wurden ebenfalls dargestellt.

     

Über die Dicyanierung der 1,4-Diaminoanthrachinone und die Reaktivität der 1,4-Diamino-9,10-dihydroanthracen-2,3-dicarbonitrile gegenüber nucleophilen Reagenzien 3. Mitteilung über Arylierungen und Heterocyclisierungen von Anthrachinonsystemen

The Dicyanation of 1,4-Diaminoanthraquinones and the Reactivity of 1,4-Diamino-9,10-dioxo-9,10-dihydroanthracene-2,3-dicarbonitriles towards Nucleophilic Reagents The reaction of 1-amino-9, 10-dioxo-4-phenylamino-9,10-dihydroanthracene-2-sulfonic acid ( 1 , R?C₆H₅) with cyanide in water yields a mixture of 1-amino-9,10-dioxo-4-phenylamino-9,10-dihydroanthracene-2-carbonitrile ( 3 , R ? C₆H₅) and 1-amino-4-(phenylamino)anthraquinone ( 4 , R ? C₆H₅) under the usual reaction conditions (Scheme 1). In dimethylsulfoxide, however, a second cyano group is introduced, and 1-amino-9,10-dioxo-4-phenylamino-9,10-dihydroanthracene-2,3-dicarbonitrile (7) is formed (Scheme 2). The cyano groups are very reactive towards nucleophiles. The cyano group in 2-position can be substituted by hydroxide and aliphatic amines (Schemes 5 and 6). The cyano group in 3-position can be eliminated by aliphatic amines and hydrazine (Scheme 7). Nucleophilic attack at the cyano C-atom of the 2-cyano group by suitable reagents leads to ring formation, yielding e.g. 2-(Δ²-1, 3-oxazolin-2-yl)-, 2-(benz[d]imidazol-2-yl)- and 2-(1H-tetrazol-5-yl)anthraquinones (Schemes 8 and 10).     

Über 4-Ureidooctahydropyrano[4,3-d]pyrimidinone

Zusammenfassung 5,6-Dihydro-2H-pyran-3-aldehyde reagieren mit Harnstoff zu 4-ureidooctahydropyrano[4,3-d]pyrimidin-2-ones. Einwirkung von Säure führt das 4-Ureidooctahydropyrano[4,3-d]pyrimidin-2-on in das 4-(2-Hydroxyäthyl)-hexahydropyrimido[4,5-d]pyrimidin-2,7-dion über.

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Heterocycles, XVIII: 4-Ureido-octahydropyrano[4,3-d]-pyrimidinones

5,6-Dihydro-2H-pyran-3-aldehydes react with urea to give 4-ureidooctahydropyrano[4,3-d]pyrimidin-2-ones. 4-Ureidooctahydropyrano[4,3-d]pyrimidin-2-one is cleaved by HCl to 4-(2-hydroxyethyl)-hexahydropyrimido[4,5-d]pyrimidin-2,7-dione.

     

Beiträge zur Chemie schwefelhaltiger Heterocyclen, 4. Mitt.: 6H-Benz[b]indeno[1,2-d]thiophen und 10H-Benz[b]indeno-[2,1-d]thiophen

Zusammenfassung Intramolekulare Cyclisierungsreaktionen von 3-Phenyl-benzo[b]thiophen-2-carbonsäurechlorid und von 2-Phenyl-benzo[b]thiophen-3-carbonsäurechlorid lieferten 6-Oxo-6H-benz[b]indeno[1,2-d]thiophen bzw. 10-Oxo-10H-benz[b]indeno[2,1-d]thiophen.

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Contributions to the chemistry of sulfur containing heterocycles, IV.: 6H-Benzo[b]indeno[1,2-d]thiophene and 10H-benzo-[b]indeno[1,2-d]thiophene

Intramolecular cyclization reactions of 3-phenyl-benzo[b]thiophene-2-carbonyl chloride and of 2-phenyl-benzo[b]-thiophene-3-carbonyl chloride gave 6-oxo-6H-benz[b]indeno-[1,2-d]thiophene and 10-oxo-10H-benz[b]indeno[2,1-d]thiophene, respectively.

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3. Mitt.:F. Sauter, Mh. Chem.99, 2100 (1968).     

Substitution reactions of phenanthro[9,10-d]triazole with benzyl chlorides

The reaction of the potassium salt of phenanthro[9,10-d]triazole and benzyl chloride gave 2-(benzyl)-2H-phenanthro[9,10-d]triazole ( 2a ) in 15% yield. The other regio-isomer, 1-(benzyl)-1H-phenanthro[9,10-d]-triazole ( 1a ), was obtained as a by-product in 3.9% yield. Similar reactions with benzyl chlorides having a methyl, a chloro or a nitro group on the aromatic ring gave the corresponding two products, 1b-j and 2b-j . In all cases, 2b-j were major products in yields of 14–62%, 1b-j were minor ones in yields of 1.4–7.6%. The structures of the isomers were confirmed by X-ray crystal analyses.     

Oxidation products of fused 2-hetarylimidazole derivatives

Oxidation of 5-(1-methyl-1H-benzimidazol-2-yl)thiophene-, and -selenophene-2-carbaldehydes with potassium dichromate in 20% aqueous sulfuric acid afforded the corresponding carboxylic acids. Analogous reaction with 5-(1-methyl-1H-benzimidazol-2-yl)furan-2-carbaldehyde led to the formation of 1-methyl-1H-benzimidazole as a result of decarboxylation of the primary oxidation product and subsequent decomposition of the furan ring. Probable factors responsible for instability of 5-(1H-benzimidazol-2-yl)-hetarene-2-carboxylic acids were considered. The oxidation of 2-furylnaphtho[2,3-d]- and 2-hetarylphenanthro-[9,10-d]imidazoles gave, respectively, an anthraquinone analog and 6,7-quinones. π-Electron-rich heterocycles in 2-furyl- and 2-pyrrolylphenanthro[9,10-d]imidazoles were oxidized completely, being replaced by hydrogen.     

Über Heterocyclen, 22. Mitt.: 3,4,6,7-Tetrahydro-5H-pyrrolo[3,4-d]pyrimidin-2(1H), 5-dione

Zusammenfassung Tetrahydro-6-brommethyl-2-oxopyrimidin-5-carbonsäureester reagieren mit Ammoniak bzw. Benzylamin zu Tetrahydro-5H-pyrrolo[3,4-d]pyrimidin-2(1H), 5-dionen. Mit 2-Aminopyridin (A) bilden sich Tetrahydro-6-(2-pyridylaminomethyl)-2-oxopyrimidin-5-carbonsäureester, Tetrahydro-5H-pyrrolo[3,4-d]pyrimidin-2(1H), 5-dione sowie 5-Äthoxycarbony]-2,3,5,6-tetrahydro-2-oxospiro(pyrimidin-4(1H), 2(3H)-1H-imidazo[1,2-a]pyridinium)bromide.

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Heterocycles XXII: 3.4.6.7-Tetrahydro-5H-pyrrolo [3.4-d]-pyrimidine-2(1H)-5-diones

Tetrahydro-6-bromomethyl-2-oxopyrimidine-5-carboxylates react with ammonia and benzylamine, resp., to give tetrahydro-5H-pyrrolo[3.4-d]pyrimidin-2(1H), 5-diones. With 2-aminopyridine (A) tetrahydro-6-(2-pyridylaminomethyl)-2-oxopyrimidine-5-carboxylates, tetrahydro-5H-pyrrolo[3.4-d]pyrimidine-2(1H). 5-diones as well as 5-ethoxycarbonyl-2.3.5.6-tetrahydro-2-oxospiro(pyrimidin-4(1H)-2(3H)-1H-imidazo[1.2-a]-pyridinium) bromides are formed.

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Herrn Prof. Dr.O. Hromatka zum 65. Geburtstag gewidmet.     

Über Dihydro-3-thioxo-3H-1,2-dithiolo[4,3-d]pyrimidin-5(4H)-one und Dihydro-3H-1,2-dithiolo[4,3-d]pyrimidin-3,5(4H)-dithione Über Heterocyclen, 34. Mitt.

Zusammenfassung Dihydro-3-thioxo-3H-1,2-dithiolo[4,3-d]pyrimidin-5(4H)-one (2) geben bei Methylierung 4-Methylderivate (2) bzw. Tetrahydro-3-methylthio-5-oxodithiolopyrimidiniumsalze (6); aus den Dithionen (3) entstehen 5-Methylthio-bzw.5-Methylthio-4-methylderivate (4) bzw. Tetrahydro-3-methylthio-5-thioxodithiolopyrimidiniumsalze (6). Peressigsäure führt2 in das Tetrahydrodithiolopyrimidiniumhydrogensulfat (10) über.2 bzw.3 geben mit Phenylhydrazin 3-Phenylhydrazone; Tetrahydro-3-methylthiodithiolopyrimidiniumjodide (6) reagieren mit Aminen bei Anwesenheit vonHMPT zu den 3-Iminoverbindungen.10 gibt mit Methylketonen und Wasserstoffakzeptoren 3-Acylmethylendihydrodithiolopyrimidin-5(4H)-one.

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Dihydro-3-thioxo-3H-1.2-dithiolo[4.3-d]pyrimidin-5(4H)-ones and dihydro-3H-1.2-dithiolo[4.3-d]pyrimidin-3,5(4H)-dithiones

Dihydro-3-thioxo-3H-1.2-dithiolo[4.3-d]pyrimidine-5(4H)-ones (2) give on methylation 4-methylderivatives (2) and tetrahydro-3-methylthio-5-oxodithiolopyrimidinium salts (6) resp.; from dithiones (3) arise 5-methylthio-resp. 5-methylthio-4-methylderivatives (4) resp. tetrahydro-3-methylthio-5-thioxo-dithiolopyrimidinium salts (6). Peracetic acid converts2 to tetrahydrodithiolopyrimidinium hydrogensulphate10. 2 and3, resp. give with phenylhydrazine 3-phenylhydrazones. Tetrahydro-3-methylthiodithiolopyrimidiniumiodides (6) react with amines in presence ofHMPT to 3-iminocompounds.10 gives with methyl ketones and hydrogen acceptors 3-acylmethylendihydro-dithiolopyrimidine-5(4H)-ones.

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Herrn Prof. Dr.E. Ziegler zum 60. Geburtstag gewidment.     

Thio-analogues of 2-(1H-Heteroarylidene)-1H-indene-1,3(2H)-diones,synthesis and formation of metal complexes

2-(1H-Heteroarylidene)-1H-indene-1,3(2H)-diones were converted into anils and dianils and then into monothio- and dithio-derivatives by treatment with hydrogen sulphide. The 2-pyridinyl monothioderivate was converted into S-alkyl ethers. In contrast with the dione1 the thio-derivatives readily formed isolable complexes with transition metals. Spectroscopic and magnetic data are reported.

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Thio-Analoge von 2-(1H-Heteroaryliden)-1H-inden-1,3(2H)-dionen. Synthese und Bildung von Metallkomplexen

Zusammenfassung 2-(1H-Heteroaryliden)-1H-inden-1,3(2 H)-dione wurden in Anile und Dianile und durch anschließende Behandlung mit Schwefelwasserstoff in die entsprechenden Mono- und Di-thio-derivate umgewandelt. Aus den 2-Pyridinyl-monothio-derivaten wurdenS-Alkyl-ether erhalten. Im Gegensatz zum Dion1 bildeten die Thioderivate glatt isolierbare Komplexe mit Übergangsmetallen. Spektroskopische und magnetische Daten werden mitgeteilt.

     

Über Dihydro-2(1H)-pyrimidinthione

Zusammenfassung 6-Alkyl-3,4-dihydro-2(1H)-pyrimidinthione sind als cyclische Alkenylthioharnstoffe der Addition von Phenolen zu 6-Hydroxyphenyltetrahydro-2(1H)-pyrimidinthionen bzw. derMannich-reaktion zu 6-Dialkylaminoäthylidentetrahydro-bzw. 6-Dialkylaminoäthyldihydro-2(1H)-pyrimidinthionen sowie zu Hexahydro-2(1H)-pyrido[4,3—d]pyrimidinthionen zugänglich. 6-Methylderivate können auch in Dihydro-6-styryl-2(1H)-pyrimidinthione bzw., in einem Fall, in ein Hexahydro-4,4-methylendi-2(1H)-pyrimidinthion umgewandelt werden.

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Dihydro-2(1H)-pyrimidinethiones (Heterocycles, XXI)

6-Alkyl-3,4-dihydro-2(1H)-pyrimidinethiones (cyclic alkenylthio carbamides) add phenoles to give 6-hydroxyphenyltetrahydro-2(1H)-pyrimidinethiones and undergoMannich reaction, to give 6-dialkylaminoethylidentetrahydro-and 6-dialkylaminoethyldihydro-2(1H)-pyrimidinethiones and hexahydro-2(1H)-pyrido[4,3—d]pyrimidinethiones, resp. 6-Methyl derivatives can also be transformed into dihydro-6-styryl-2(1H)-pyrimidinethiones resp., in one case, into a hexahydro-4,4-methylendi-2(1H)-pyrimidinethione.

     

Naturstoffchemie, 174. Mitt. [1]: Oxidation von Acronycin mit Kaliumpermanganat

Zusammenfassung Die Oxidation des Acridonalkaloids Acronycin (1) mit Kaliumpermanganat führt zu (1S-cis)-1,2,3,12-Tetrahydro-1,2-dihydroxy-6-methoxy-3,3,12-trimethyl-7-H-pyrano[2,3-c]acridin-7-on (2), 1-Hydroxy-6-methoxy-3,3,12-trimethyl-1H-pyrano[2,3-c]acridin-2,7(3H,12H)-dion (3) und 1-Hydroxy-6-methoxy-3,3,12-trimethyl-1-(2-oxopropyl)-1H-pyrano[2,3-c]acridin-2,7(3H,12H)-dion (4).

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Natural product chemistry, part. 174 [1]: Oxidation of acronycine by potassium permanganate

Summary Oxidation of the acridone alkaloid acronycine (1) by potassium permanganate results in oxidation of the cromenering to give (1S-cis)-1,2,3,12-tetrahydro-1,2-dihydroxy-6-methoxy-3,3,12-trimethyl-7H-pyrano[2,3-c]acridine-7-one (2), 1-hydroxy-6-methoxy-3,3,12-trimethyl-1H-pyrano-[2,3-c]acridine-2,7(3H,12H)-dione (3) and 1-hydroxy-6-methoxy-3,3,12-trimethyl-1-(2-oxopropyl)-1H-pyrano[2,3-c]acridine-2,7(3H,12H)-dione (4).

     

Structures of 1‐hydrophenanthroimidazoles: building blocks in the synthesis of expanded‐ring bis(imidazoles)

The structures of 1H‐phenanthro[9,10‐d]imidazole, C₁₅H₁₀N₂, (I), and 3,6‐dibromo‐1H‐phenanthro[9,10‐d]imidazole hemihydrate, C₁₅H₈Br₂N₂·0.5H₂O, (II), contain hydrogen‐bonded polymeric chains linked by columns of π–π stacked essentially planar phenanthroimidazole monomers. In the structure of (I), the asymmetric unit consists of two independent molecules, denoted (Ia) and (Ib), of 1H‐phenanthro[9,10‐d]imidazole. Alternating molecules of (Ia) and (Ib), canted by 79.07 (3)°, form hydrogen‐bonded zigzag polymer chains along the a‐cell direction. The chains are linked by π–π stacking of molecules of (Ia) and (Ib) along the b‐cell direction. In the structure of (II), the asymmetric unit consists of two independent molecules of 3,6‐dibromo‐1H‐phenanthro[9,10‐d]imidazole, denoted (IIa) and (IIb), along with a molecule of water. Alternating molecules of (IIa), (IIb) and water form hydrogen‐bonded polymer chains along the [110] direction. The donor–acceptor distances in these N(imine)...H—O(water)...H—N(amine) hydrogen bonds are the shortest thus far reported for imidazole amine and imine hydrogen‐bond interactions with water. Centrosymmetrically related molecules of (IIa) and (IIb) alternate in columns along the a‐cell direction and are canted by 48.27 (3)°. The present study provides the first examples of structurally characterized 1H‐phenanthroimidazoles.     

Some novel heterocyclic systems derived from 7-amino-2,3-dihydro-8-nitro-1H-pyrrolo[1,2-α]benzimidazole and the corresponding diamine

The preparation of 7-amino-2,3-dihydro-8-nitro-1H-pyrrolo[1,2-a]benzimidazole from 1,4-diacetamido-2,3-dinitrobenzene is described. Reaction of this compound with 2,5-dimethoxytetrahydrofuran produces 2,3-dihydro-8-nitro-7-N-pyrrolo-1H-pyrrolo[1,2-a]benzimidazole, which can be cyclised to produce two new heterocyclic ring systems, 9,10-dihydro-8H-pyrrolo[1,2-a]pyrrolo(1′,2′:1,2]imidazo[5,4-f]quinoxaline and 9,10-dihydro-8H-pyrrolo[2,1-c]pyrrolo[1′,2′:1,2]imidazo[4,5-h][1,2,4]benzotriazine. The corresponding diamine, 7,8-diamino-2,3-dihydro-1H-pyrrolo[1,2-a]benzimidazole undergoes a variety of condensation reactions to produce several new heterocyclic systems, for example, with formic acid, 1,7,8,9-tetrahydroimidazo-[4,5-e]pyrrolo[2,1-6]benzimidazole is formed and with diacetyl, 9,10-dihydro-2,3-dimethyl-8H-pyrrolo-[1′,2′:1,2]imidazo[5,4-y]quinoxaline is obtained.     

Über die Synthese von 5-Phenyl-1H-thieno[2,3-e]-1,4-diazepin-2(3H)-onen

Zusammenfassung Es wird die Synthese des 5-Phenyl-1H-thieno[2,3-e]-1,4-diazepin-2(3H)-ons (5), seine Alkylierung in Stellung 1, seine Chlorierung und Nitrierung in Stellung 7 und die N-Oxid-Bildung (in Stellung 4) beschrieben.

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Synthesis of 5-phenyl-1H-thieno[2.3-e]1.4-diazepin-2(3H)-ones

The preparation of 5-phenyl-1H-thieno[2.3-e]1.4-diazepin-2(3H)-one (5), its alkylation in position 1, its chlorination and nitration in position 7 and the N-oxide formation (in position 4) are described.

     

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.

     

K-region oxides and imines of benzo[b]phenanthro[2,3-d]thiophene and benzo[b]phenanthro[3,2-d]thiophene

The syntheses of the K-oxides and K-imine derivatives of benzo[b]phenanthro[2,3-d]thiophene and benzo-[b]phenanthro[3,2-d]thiophene are described. The parent hydrocarbons 1 and 2 were oxidized with osmium tetroxide and sodium metaperiodate, and the dialdehydes 12 and 18 so formed, cyclized to the corresponding epoxides 1a,12b-dihydrobenz[b]oxireno[9,10]phenanthro[2,3-d]thiophene ( 7 ) and 1a,12b-dihydrobenz-[b]oxireno[9,10]phenanthro[3,2-d]thiophene ( 13 ). Reaction of the oxiranes with sodium azide gave mixtures of azido-alcohols that, in turn, were transformed to the thiaarene imines 1a,12b-dihydro-1H-benz[b]azirino-[9,10]phenanthro[2,3-d]thiophene ( 8 ) and 1a,12b-dihydro-1H-benz[b]azirino[9,10]phenanthro[3,2-d]thiophene ( 14 ), respectively, with the aid of tri-n-butylphosphine.     

Natural product chemistry. Part 116. Synthesis of daurine and folidine: Two 2(1H)-quinolinone alkaloids fromHaplophyllum species

Structures of the recently isolated 2(1H)-quinolinone alkaloids, daurine and folidine have been confirmed by total synthesis.

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Naturstoffchemie. 116. Mitt.: Synthese des Daurins und Folidins, 2(1H)-Chinolinon-Alkaloide aus Haplophyllum Spezies

Zusammenfassung Die Strukturen der kürzlich aufgefundenen 2(1H)-Chinolinon-Alkaloide Daurin und Folidin konnten durch Totalsynthese bestätigt werden.