Eine neue Azepinring-Synthese

A New Azepine-Ring Synthesis A new one-step synthesis of an azepine ring is described. The 2H-pyran-2-one ring of methyl cumalate ( 8 ) or cumalaldehyde ( 2 ) upon reaction with an 1-aminoacryl derivative, e.g. 1 or 6 , is opened with subsequent decarboxylation to give a 1-aminobutadiene derivative that undergoes an electrocyclic ring closure to the azepine ring (Schemes 1 and 2).     

Beiträge zur Chemie schwefelhaltiger Heterocyclen, 3. Mitt.: Ringschlußreaktionen zu N-substituierten 2-Aminomethyl-Derivaten des 4-Oxo-3,4,5,6,7,8-hexahydro-benzo[b]thieno-[2,3-d]pyrimidins

Zusammenfassung Eine Gruppe von [2-Acylamino-4,5,6,7-tetrahydro-benzo[b]-thienyl-(3)]-carbonsäureamiden mit einem basischen Rest am Substituenten der 2-Stellung wurde nach zwei Methoden zu entsprechend substituierten 2-Alkyl-4-oxo-3,4,5,6,7,8-hexahydro-benzo[b]thieno[2,3-d]pyrimidinen cyclisiert. Die Herstellung der Ausgangsmaterialien erfolgte durch Umsetzung von [2-Chloracetylamino-4,5,6,7-tetrahydro-benzo[b]thienyl-(3)]-carbonsäureamid mit sekundären Aminen bzw. Benzylamin.

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A series of [2-acylamino-4,5,6,7-tetrahydro-benzo[b]thienyl-(3)]-carboxamides with a basic group in the substituent at position 2 was cyclized by two methods to the corresponding substituted 2-alkyl-4-oxo-3,4,5,6,7,8-hexahydro-benzo[b]thieno-[2,3-d]pyrimidines. The starting materials were prepared by reaction of [2-chloracetylamino-4,5,6,7-tetrahydro-benzo[b]-thienyl-(3)]-carboxamide with secondary amines or benzylamine.

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Mitt.:F. Sauter, Mh. Chem.99, 1591 (1968).     

Cycloadditions of nitrile oxides and nitrones to 4,4-methylene-1-methylpiperidine: Studies in regio- and stereoselectivity

Summary A series of spiro-substituted isoxazole derivatives were synthesized by 1,3-dipolar cycloadditions of nitrile oxides and nitrones to 4,4-methylene-1-methylpiperidine. Since nmr studies confirmed that only one regioisomer was formed selectively, semi-empirical quantum mechanical methods (AM1) were used to rationalize this regiochemical preference via calculation and inspection of HOMO-LUMO-energy and coefficients. X-ray structure analysis carried out for one of these products showed the occurrence of only one stereoisomer, explicable by comparing AM1-calculated H _f -values of all possible cycloadducts.Part XXXI in the series 1,3-Dipolar Cycloaddition on Heterocycles. Part XXX [Ref. 5]     

Fused silica capillary column GC/MS for the analysis of priority pollutants

Operational characteristics have been determined for fused silica capillary column (FSCC) GC/MS as applied to “extractable” priority polutants. Chromatographic data show excellent relative retention time (RRT) intralaboratory precision and interlaboratory accuracy when multiple internal standards are empolyed. Potential chromatographic problems, such as column overload and “double peaking”, are addressed. Response factor relative standard deviations (RSD) at 50 ng for most of the extractable priority pollutants over the long term indicated precise determination (i.e. RSD generally ≤ 10%). Linearity was demonstrated over two orders of magnitude for FSCC GC/MS analysis of compounds with relatively low and high RF (response factor) values. Potential quantitative problems, such as saturation, are discussed. For certain aromatic priority pollutants interlaboratory RF agreement was observed. This was noted as perhaps the most important property of FSCC GC/MS analysis when the multiple internal standard approach is utilized. Determinations of extractable priority pollutants are directly compared for paced column GC/MS and FSCC GC/MS analysis of separate and composited extracts. For six extracts analyzed in triplicate, the latter configuration was shown to produce more consistent results. In view of the superior analysis logistics of composite extract FSCC GC/MS analysis, this approach was established as the preferred method for the analysis of priority pollutants classified as extractable.     

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.     

Synthesen der 2-Phenyl-benzo[b]thiophen-3-carbonsäure

Zusammenfassung 2-Phenyl-benzo[b]thiophen-3-carbonsäure (4) wurde auf zwei verschiedenen Wegen hergestellt: durch Umsetzen von Thionaphthenchinon mit -Chlor-phenylessigsäure und Ringschlußreaktionen der als Zwischenprodukt isolierten o-(-Carboxybenzylthio)-phenylglyoxylsäure (2) und durch Einführung einer Carboxylgruppe in das 2-Phenyl-benzo[b]thiophen über die durch N-Bromsuccinimid erhältliche 3-Bromverbindung (6) und anschließendeGrignardreaktion.Zusätzlich wird die Darstellung von zwei basischen Derivaten beschrieben.

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Syntheses of 2-phenyl-benzo[b]thiphene-3-carboxylic acid

2-Phenyl-benzo[b]thiophene-3-carboxylic acid was prepared on two different ways: by reaction of thionaphthenequinone with -chloro-phenylacetic acid followed by cyclizations of the o-(-carboxybenzyl-thio)-phenylglyoxylic acid, isolated as an intermediate, and by introduction of a carboxyl group into 2-phenyl-benzo[b]thiophene via the 3-bromo compound (prepared by means ofNBS) and aGrignard reaction.Additionally the preparation of two basic derivatives is described.

     

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).     

Reaktionen des Cumalinsäure-methylesters und Cumalinaldehyds mit ambidenten Nucleophilen

Reactions of Methyl Coumalate and Coumalaldehyde with Ambident Nucleophiles Methyl coumalate and coumalaldehyde show great diversity in their reactions with ambident nucleophiles both depending upon the 2H-pyran-2-one derivative and the nature of the ambident nucleophile used. The products are either pyridine or pyrimidine derivatives.     

Derivate des 3-Phenyl-benzo[b]thiophens

Zusammenfassung 2-Methylthio-benzophenon reagierte mit Chloressigsäure zu 3-Phenyl-benzo[b]thiophen-2-carbonsäure und mit -Chlorphenylessigsäure zu 2,3-Diphenyl-benzo[b]thiophen. 3-Phenyl-5-methoxy-benzo[b]thiophen-2-carbonsäure wurde aus 3-Phenyl-5-amino-benzo[b]thiophen-2-carbonsäure durch Verkochen des Diazoniumsalzes und Methylierung erhalten; ihr N-Methylpiperazid sowie 3 basisch substituierte Ester wurden dargestellt.

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Derivatives of 3-phenylbenzo[b]thiophene

2-Methylthio-benzophenone reacted with chloroacetic acid to 3-phenyl-benzo[b]thiophene-2-carboxylic acid and with -chloro-phenylacetic acid to 2,3-diphenyl-benzo[b]thiophene. 3-Phenyl-5-methoxy-benzo[b]thiophene-2-carboxylic acid was prepared by diazotation of 3-phenyl-5-amino-benzo[b]thiophene-2-carboxylic acid and hydrolysis to the hydroxy compound followed by methylation; its N-methylpiperazide and three esters with basic substituents were synthesized.