Synthese von basisch substituierten Thiazolo[3,2—a]thieno[2,3—d]-pyrimidinen

Addition of Br₂ to the exocyclic double bond of 2-methylene-2.3-dihydro-thiazolo[3.2?a]thieno[2.3?d]pyrimidine-5-ones and-[1]benzothieno[2.3?d]pyrimidine-5-ones, followed by elimation of HBr gave the corresponding 2-bromomethylthiazolo-compounds, which reacted with secondary amines to 2-(dialkylamino-methyl)-thiazolo[3.2?a]-([1]-benzo)-thieno-[2.3?d]pyrimidine-5-ones and their heterocyclic analogues.     

Synthese von basisch substituierten 2- bzw. 3-Phenyl-benzo[b]thiophen-1,1-dioxiden

3-Halogeno-2-phenyl-benzo[b]thiophene-1.1-dioxide and 2-bromo-3-phenyl-benzo[b]thiophene-1.1-dioxides reacted with open-chain and heterocyclic amines to the corresponding title substances.     

Synthese von 2-Methylen-2,3-dihydro- und 2-Methyl-5H-thiazolo[3,2—a]thieno[2,3—d]pyrimidinen

The title substances and their [1]benzothieno analogues were synthesized by reaction of 3-allyl-2-mercapto-([1]benzo)thieno-[2.3—d]pyrimidine-4(3H)-ones with Br₂ to 2-bromomethyl-2.3-dihydro-thiazolo[3.2—a]([1]benzo-)thieno[2.3—d]pyrimidine-5-ones, which on treatment with morpholine did not give the corresponding morpholine derivatives but elimination to the exocyclic double bond. These 2-methylene-2.3-dihydro-products were isomerized by H₂SO₄ to the corresponding 2-methyl compounds.     

Zur Synthese von 4-Aryl-5,6-dihydro-benzo[h]chinolinen

A new route to the benzo[h]quinoline system3 byMichael-addition of malononitrile to 2-arylidene-1-tetralones1 is presented. The mechanism of this reaction is elucidated by isolation of the intermediate 4H-naphtho[1,2—b]-pyrane2 and its reaction to3. The reaction is proposed to be a sequence of addition, cyclisation,Dimroth-rearrangement and disproportionation.

1. Mitt.:H.-H. Otto, Arch. Pharm. [Weinheim]307, 444 (1974).     

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.     

Synthese von Furo [2,3-b]chinolinen

A new route to furo[2,3-b]quinolines has been developed based on the use of N-arylaconamides as starting materials. These anilides when heated with polyphosphoric acid, readily underwent intramolecular cyclization to furnish the respective 1,2-dihydro-2-oxo-quinoline-3-acetic acids which were then transformed into the corresponding dihydrofuro[2,3-b]quinolines by literature procedures. Sequential treatment of the dihydro compound withNBS andDBU afforded the corresponding furo[2,3-b]quinoline. The NMR spectra of the furoquinolines are discussed.

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Mitt.: siehe Lit.     

Synthese von [1]Benzothieno[2,3—c]pyrazol-Derivaten

Derivatives of [1]benzothieno[2.3-c]pyrazole, a new heterocyclic ring system, were synthesized by 1.3-dipolar cycloadditions: benzo[b]thiophene-1.1-dioxide and derivatives thereof reacted with diazomethane and diazoethane to yield substituted [1]benzothieno[2.3-c]pyrazolines. A similar reaction with ethyl diazoacetate gave the corresponding cyclopropa[b][1]benzothiophene-2.2-dioxide derivative.     

Synthese von [1]Benzothieno[2,3—d]isoxazol-Derivaten

Derivatives of [1]benzothieno[2.3—d]isoxazole, a new heterocyclic ring system, were synthesized by 1.3-dipolar cyclisations: benzo[b]thiophene-1.1-dioxide and its 3-methyl derivative reacted with nitrile oxides and nitrones to the corresponding substituted [1]benzothieno[2.3—d]isoxazolines and-isoxazolidines. Hydrogenolysis of the latter cleaved the isoxazolidine ring, yielding the corresponding 2-(-phenylamino-benzyl)-3-hydroxy-2.3-dihydro-benzo[b]thiophene-1.1-dioxides.

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Mit 1 Abbildung

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Herrn Prof. Dr.E. Hardegger zum 60. Geburtstag gewidmet.     

Synthese von 2,4-Diamino-thieno[2,3-d]pyrimidin-Derivaten

Synthesis of 2,4-Diamino-thieno[2,3-d]pyrimidines Condensation of 2-aminothiophene-3-carbonitrile ( 4 ) with guanidine or sequential addition of CS₂ and NH₃ to 4 provides 2,4-diaminothieno[2,3-d]pyrimidine ( 7 ). This compound yields, after sequential addition of sec-BuLi and either [3-(trifluoromethyl)benzene]sulfenyl chloride ( 8 ) or the corresponding disulfide 9 , followed by acidic work up, 2,4-diamino-6-{[3-(trifluoromethyl)phenyl]thio}thieno[2,3-d]pyrimidine ( 10 ). In another approach, 2-amino-5-{[3-(trifluoromethyl)phenyl]thio}thiophene-3-carbonitrile ( 11 ) obtained from 4 and 8 is transformed to 10 by condensation with guanidine. Corresponding to the second route, 2,4-diamino-6-[(naphth-2-yl)thio]thieno-[2,3-d]pyrimidine ( 16 ) is synthesized. Oxidation of 10 with m-chloroperbenzoic acid gives 2,4-diamino-6-{[3-(tri-fluoromethyl)phenyl]sulfinyl}thieno[2,3-d]pyrimidine ( 13 ).     

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.

     

Synthese von Thieno[2,3—f]chinolin-Derivaten

Catalytic hydrogenation of 2.3-dihydro-thieno[2.3?f]-quinoline-1.1-dioxide yielded 2.3.6.7.8.9-hexahydrothieno-[2.3?f]quinoline-1.1-dioxide, which was substituted via the corresponding chloroacyl compounds to several 6-aminoacyl-derivatives.Skraup's synthesis using 6-amino-2.3-dihydro-3-morpholino-benzo[b]thiophen-1.1-dioxide gave 2.3-dihydro-3-morpholino-thieno[2.3?f]quinoline.     

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

Zusammenfassung Es wird die Synthese von in Stellung 6 und 7 mono- und dimethylsubstituierten 5-Phenyl-1H-thieno[2,3-e]1,4-diazepin-2(3H)-onen und ihre Methylierung in Stellung 1 beschrieben. Das Thienodiazepin5 b wurde außerdem in Stellung 7 chloriert, bromiert und nitriert.

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

The preparation of in position 6 and 7 mono- and dimethylsubstituted 5-phenyl-1H-thieno[2.3-e]1.4-diazepin-2(3H)-ones and their methylation in position 1 are described. The thienodiazepine5 b was furthermore chlorinated, brominated and nitrated in position 7.

     

Synthese von substituierten Pyridiniumsalzen

Derivatives of bis-pyridinium salts—new bifunctional pyridinium perchlorates and monofunctional pyridinium-salts derived from sulfonamides and heterocyclic systems—were synthesized by reaction of pyrylium salts with diamines or monoamino-heterocycles.     

Über die Synthese von substituierten Thieno[3,4—b]chinolin-9(4H)-onen

The synthesis of in position 4 substituted thieno[3.4-b]quinoline-9(4H)-ones (6) by aromatization of 1.4-dihydrothieno[3.4-b]quinoline-9(3H)-ones (4) and attempts to cyclize 4-phenylamino-3-thiophenecarboxylic acid (3c), or derivatives thereof, to compounds of type6 are described.