Synthesen von heterocyclen, 143. Mitt.: Eine Synthese von Oxazolo[3,2-a]chinolinen

Zusammenfassung Substituierte 3,4-Dihydrocarbostyrile reagieren mit Oxalylchlorid zu den entsprechenden Oxazolo[3,2-a]chinolinen, während mit monosubstit. Malonylchloriden N-Acylierung stattfindet.

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Syntheses of heterocycles CXLIII: A synthesis of oxazolo-[3.2-a]quinolines

Substituted 3.4-dihydro-carbostyriles react with oxalyl chloride to give the corresponding oxazolo[3.2-a]quinolines1–3, while monosubstituted malonyl chlorides yield N-acylated carbostyrils.

     

Synthesen von 4-Amino-thieno[2,3—b]pyridinen

The Cyclization of 2-(1,1-dicyanovinylamino)-thiophenes2 by treatment with AlCl₃ yield 4-amino-5-cyano-thieno[2,3-b]pyridines3. 2-(1-acylvinyl-amino)-3-cyano-thiophenes7, obtainable from 2-amino-3-cyano-thiophenes and -diketones, react in the presence of AlCl₃ to form 4-acylamino-thieno[2,3-b] pyridines8. This reaction is connected with the transfer of the acyl group from C- to the N-atom. 4-Amino-5-cyano-thieno[2,3-b]pyridones-(6)11 are synthesized from 2-amino-3-cyano-thiophenes and ethyl cyano acetate in the presence of sodium ethoxide.

     

Synthesen von Heterocyclen, 95. Mitt.: Chinolizine und Indolizine I: Eine Synthese von 2-Hydroxychinolizinonen-(4)

Zusammenfassung An der Methylgruppe substituierte -Picoline, insbesondere 2-Pyridylessigsäurederivate, reagieren mit unsubstit. oder monosubstit. Malonsäure-bis-trichlorphenylestern, Malonsäurechloriden oder Kohlensuboxid zu 2-Hydroxychinolizinonen-(4), die katalytisch zu 2-Hydroxy-6,7,8,9-tetrahydrochinolizinonen-(4) hydriert werden können.

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2-Alkylpyridines, especially derivatives of 2-pyridineacetic acid, react with unsubstituted and monosubstituted 2.4.6-trichlorophenyl malonates or malonyl chlorides or C₃O₂ to derivatives of 2-hydroxy-quinolizin-4-one. These compounds are hydrogenated in acetic acid in the presence of palladium to 2-hydroxy-6.7.8.9-tetrahydro-quinolizin-4-ones.

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Mit 2 Abbildungen.

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Herrn Prof. Dr.F. Wessely zum 70. Geburtstag gewidmet.     

Synthesen von basisch substituierten ([1]Benzo-)Thieno-[2,3—d]pyrimidin-Derivaten und von ([1]Benzo-)Thieno-[2,3-d]-1,2,4-triazolo[4,3-a]pyrimidin-Derivaten

Reaction of 2-methylthio-thieno[2.3-d]pyrimidin-4(3H)-ones with heterocyclic secondary amines, ethanolamine and hydrazine, resp., gave the corresponding derivatives with a basic substituent in position 2. Cyclization of the hydrazino compounds with formic acid gave derivatives of thieno[2.3-d]-1.2.4-triazolo[4.3-a]pyrimidine and [1]benzothieno[2.3-d]-1.2.4-triazolo[4.3-a]pyrimidine, two new heterocyclic systems.     

Synthesen von Heterocyclen, 90. Mitt.: Eine Synthese von subst. 4-Hydroxy-pyridonen-(2)

Zusammenfassung Propiophenon-imin bzw. Campher-imin reagieren mit monosubstit. Malonsäurechloriden zu Derivaten des 4-Hydroxypyridons-(2).

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Propiophenone-imine and camphorimine react with monosubstituted malonyl chlorides to derivatives of 4-hydroxy-pyrid-2-one.

     

Beiträge zur Chemie schwefelhaltiger Heterocyclen, 1. Mitt.: Synthesen von Benzo[b]thieno[2,3−d]pyrimidin-Derivaten

Zusammenfassung 4-Oxo-3,4,5,6,7,8-hexahydro-benzo[b]thieno[2,3–d]pyrimidin sowie die 2-Methyl- und 2-Phenyl-Derivate davon wurden durch Ringschlußreaktionen aus 2-Acylamino-4,5,6,7-tetrahydrobenzo[b]thienyl-(3)-carbonsäureamiden gewonnen; das 2-Phenyl-Produkt entstand auch durch thermische Cyclisierung von 2-Benzylidenamino-4,5,6,7-tetrahydro-benzo[b]-thienyl-(3)-carbonsäureamid.

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4-Oxo-3,4,5,6,7,8-hexahydro-benzo[b]thieno[2,3–d]pyrimidine as well as its 2-methyl and 2-phenyl derivatives were synthesized by cyclization of the corresponding 2-acylamino-4,5,6,7-tetrahydro-benzo[b]thienyl-(3)-carboxamides; the 2-phenyl compound was also prepared by thermal cyclization of 2-benzylideneamino-3-carbamoyl-4,5,6,7-tetrahydro-benzo[b]thienyl-(3)-carboxamide.

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Mit 1 Abbildung     

Synthese und Eigenschaften von Thiazolo[3,2-a]pyrimidinen und Thiazolo [3,2-a] pyrrolo [2,3-d]pyrimidinen

From the alkali-catalysed reaction of thiouracil with bromoacetaldehyde diethyl acetal three products are isolated in nearly the same quantity: 2-(2, 2-diethoxyethylthio)-uracil ( 2 ) and two cyclization products: 3 , a thiazolo[3, 2-a]pyrimidin-5-one, and 4 , athiazolo[3, 2-a]pyrimidin7-one. By warming with acid both 2 and 4 yield 3 . Rearrangement of 4 to 3 proceeds also by heating the hydrochloride. Similar cyclizations leading to thiazolo[3, 2-d]pyrrolo[2, 3-d]pyrimidin-5-ones are also described. Bromine substitutes 3 in position 6. The bromo derivative 6 on treatment with primary or secondary amines affords 7-amino compounds.     

Heterocyclen, 73. Mitt.: Synthesen einiger substituierter 1,3,5-Triazine und Imidazo[1,2-a]-[1,3,5]-triazine

Zusammenfassung Substituierte 1,3,5-Triazine mit verschiedenen funktionellen Gruppen wurden synthetisiert und einige Azido-1,3,5-triazine wurden aufeine denkbare Azido—Tetrazol-Valenz-Isomerisierung untersucht; nur die Azid-Form konnte jedoch nachgewiesen werden. Von einigen Amino-1,3,5-triazinen ausgehend, gelang die Synthese von substituierten Imidazo[1,2-a]-[1,3,5]-triazinen.

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Heterocycles, LXXIII: Synthesis of some substituted 1.3.5-triazines and imidazo[1,2-a]-[1.3.5]-triazines

The synthesis of 1.3.5-triazines carrying various functional groups is described. 1.3.5-triazines with azido groups were studied for possible azido-tetrazolo valence isomerization; however, only the azido form could be detected. Some amino-1.3.5-triazines were used as starting material for the synthesis of substituted imidazo[1,2-a]-[1.3.5]-triazines. *** DIRECT SUPPORT *** A3615139 00009

     

Synthesen von Heterocyclen, 121. Mitt.: Chinolizine und Indolizine V: Eine Synthese von 4-Methyl-2-chinolizinonen

Zusammenfassung Die Reaktion von 2-Pyridylessigsäurederivaten (1a, 1b) mit Diketen (2) in sied. Eisessig liefert in 1-Stellung substit. 4-Methyl-2-chinolizinone.

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Syntheses of heterocycles, CXXI: Quinolizines and indolizines. A synthesis of 4-methyl-2-quinolizinones

The reaction of 2-pyridylacetic acid derivatives (1a, 1b) with diketene (2), gives 4-methyl-2-quinolizinones.

     

Synthesen und Kristallstrukturen von [Pd9As8(PPh3)8] und [Pd9Sb6(PPh3)8]

Syntheses and Crystal Structures of [Pd₉As₈(PPh₂)₈] and [Pd₉Sb₆(PPh₃)₈] [PdCl₂(PPh₃)₂] reacts with As(SiMe₃)₃ to give the new cluster [Pd₉As₈(PPh₃)₈] ( 4 ). 4 has been characterized by X-ray crystal structure analysis. It is a molecule in which four [Pd₂(PPh₃)₂]-units are bridged by As₂-units. A further Pd atom is located in the centre of the cluster. 4 crystallizes in the space group C2/c with four formula units per unit cell. The lattice constants at 200 K are: a = 3 970.6(3), b = 1 648.90(16), c = 3 266.30(20) pm, β = 131,44(4)°. The reaction of [PdCl₂(PPh₃)₂] with Sb(SiMe₃)₃ yields [Pd₉Sb₆(PPh₃)₈] ( 5 ). 5 consists of a body centred cubic Pd₉-cluster. All of the cube faces are capped by μ₄-Sb-ligands. 5 crystallizes in the space group Pn3 with two formula units per unit cell. The lattice constants at 200 K are: a = b = c = 1 995.4(2) pm.     

Synthesen von Heterocyclen, 88. Mit.: Eine Synthese von N-Aryl-4-hydroxy-5,6-polymethylenpyridonen-(2)

Zusammenfassung Anile cyclischer Ketone reagieren mit monosubstituierten Malonsäurechloriden zu N-Aryl-4-hydroxy-5,6-polymethylenpyridonen-(2).

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The reaction of cyclic ketones with monosubstituted malonyl chlorides yields N-aryl-4-hydroxy-5,6-polymethylen-pyrid-2-ones.

     

Synthesen von Heterocyclen, 99. Mitt.: Chinolizine und Indolizine IV: Eine Synthese von Hydroxy-benzochinolizinonen

Zusammenfassung An der Methylgruppe substituierte Chinaldine (1) reagieren mit monosubstit. Malonsäure-bis-2,4,6-trichlorphenylestern (2a-c) bei 250° zu Derivaten des Hydroxy-benzo[c]chinolizinons (4bzw.5). Aus Chinaldin selbst entstehen unter diesen Bedingungen Pyrono-chinolizinone (3). Analog erhält man bei der Umsetzung von 1-Methylisochinolin (9) mit2 2-Hydroxy-benzo[a]chinolizin-4-one (11) und aus 6-Alkylphenanthridinen (13) Dibenzoderivate des Chinolizinons (14). 2-Chinolylessigsäureester (6) addiert sogar Kohlensuboxid (C₃O₂) unter Bildung von 4-Äthoxy-carbonyl-3-hydroxy-benzo[c]chinolizin-1-on (8 a).

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2-Alkylquinolines (1) react with monosubstituted 2.4.6-trichlorophenyl malonates (2) at 250° to derivatives of hydroxy-benzo[c]quinolizinone (4 or5). The reaction of quinaldine itself with2 leads to pyrono-quinolizinones (3). The reaction of2 with 1-methylisoquinoline (9) yields 2-hydroxy-4H-benzo[a]quinolizin-4-ones11, and with 6-alkyl-phenanthridines (13) dibenzo[a, c]quinolizinones (14) are obtained. Carbon suboxide (C₃O₂) is added readily to ethyl 2-quinolyl acetate (6) yielding 4-ethoxy-carbonyl-3-hydroxy-1H-benzo[c]quinolizin-1-one (8 a).

     

Synthesen und Charakterisierung von [Ni(tBuAs)6] und [Pd(tBuAs)6]

Syntheses and Characterization of [Ni(tBuAs)₆] and [Pd(tBuAs)₆] The reduction of tBuAsCl₂ with magnesium in the presence of NiCl₂ or PdCl₂ yields the complexes [Ni(tBuAs)₆] ( 2 ) and [Pd(tBuAs)₆] ( 3 ). The structure of ( 2 ) was determined by X-ray single crystal structure analysis. ( 2 ) consists of the sixmembered ring (tBuAs)₆ in chair conformation with the nickel atom in the center of this ring.     

Heterocyclen, 48. Mitt.: Synthesen von substituierten 1,3,5-Triazinen und über eine neuartige Synthese substituierters-Triazolo[4,3-a] 1,3,5-triazine

Zusammenfassung Durch stufenweisen Austausch von Chloratomen im 2,4,6-Trichlor-1,3,5-triazin wurden verschiedene unsymmetrisch substituierte Derivate des 1,3,5-Triazins synthetisiert. Von einigen Hydrazinotriazinen ausgehend gelang die Synthese von substituiertens-Triazolo[4,3-a]-1,3,5-triazinen.

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By a successive replacement of the chlorine atoms in 2.4.6-trichloro-1.3.5-triazine it was possible to synthesize different unsymmetrically substituted derivatives of 1.3.5-triazine. Some hydrazino triazines were used as starting material for the synthesis of substituteds-triazolo[4.3-a]-1.3.5-triazines.