Halogenbenzaldehyde, 3. Mitt.

Zusammenfassung Mittels der Konversion aromatischer Amine in die entsprechenden Benzaldehyde, einer Methode, die vonBeech entwickelt und von uns auf Haloaniline erweitert wurde, werden in einfacher, eleganter Weise zwei Halogenbenzaldehyde dargestellt.2. Mitt.:S. D. Jolad undS. Rajagopal, Naturwiss.48, 645 (1961).     

Thalidomid-Analoga, 3. Mitt.

Zusammenfassung Zur Untersuchung möglicher Struktur-Wirkungs-Beziehungen in der Reihe der verbrückten Thalidomid-Analoga wurden 36 offenkettige und verkürzte Abkömmlinge der Testsubstanz K 2004 (2) synthetisiert. Die pharmakologische Untersuchung der hergestellten Verbindungen ergab in keinem Falle eine signifikante sedative Aktivität. Dies legt den Schluß nahe, daß die intakte Glutarimid-Struktur bei1 und2 für das Zustandekommen der schlafinduzierenden Wirkung unentbehrlich ist.

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Thalidomide analogues

For the evaluation of possible structure-activity relationships in the series of bridged thalidomide analogues 36 openchain and shortended congeners of the test substance K 2004 (2) have been synthesized. The pharmacological evaluation of these compounds revealed in no case any significant sedative activity. This leads to the conclusion that the intact glutarimide structure must be essential for the sleep-inducing activity of1 and2.

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Herrn Prof. Dr.M. Pailer zum 60. Geburtstag gewidmet.     

Functional polymers. VI. Preparation and polymerization of methyl 3-vinylsalicylate,methyl 3-vinylacetylsalicylate, 3-vinylsalicylic acid,and 3-vinylacetylsalicylic acid

The title compounds were synthesized and their homopolymerizations and copolymerizations with styrene and a number of acrylic monomers were investigated. Methyl 3-vinylacetylsalicylate was prepared in a five-step synthesis from 2-ethylphenol in an overall yield of 40%. Methanolysis of this compound gave methyl 5-vinylsalicylate in 63% yield. Hydrolysis of methyl 3-vinylsalicylate gave a nearly quantitative yield of 3-vinylsalicylic acid which could be acetylated to 3-vinylacetylsalicyclic acid (3-vinyl aspirin). 3-Vinylsalicylic acid derivatives were readily homopolymerized and copolymerized with styrene, methyl methacrylate, and methacrylic acid, and 3-vinylsalicyclic acid was copolymerized with a number of vinyl and acrylic monomers. Copolymer compositions were determined by examination of ¹H-NMR spectra.     

Stereochemie planar-chiraler Verbindungen, 3. Mitt.

1.6-Methano[10]anulene-2-carboxylic acid (6) was resolvedvia its salts with (+)-and (?)-α-phenethylamine, resp. Two crystallisations from ethanol gave optically pure6 ([α] _D ²⁰ = 250°) as has been shown by application of theNMR-method to the mixture of the diastereomeric phenethylamides of6. Starting from (+)-6 several optically active methano[10]anulenes were prepared and theirCD-spectra recorded. Amongst these are the 2-acetyl, formyl and methyl derivatives and theendo-carbinol14a accessible from the acetyl compoundvia the cyclic ketone13. The absolute configurations of all compounds were established as being (S)_p by kinetic resolutions both of the anhydride of6 with (?)-phenethylamine and of14 a with (+)-α-phenylbutyric anhydride. The applicability ofHoreau's method to compounds of type14 was checked with (+)(R)phenyl-vinyl carbinol.     

Reaktionen mit Dimethylformamid, 3. Mitt.

Zusammenfassung Die Umsetzung von Dimethylformamid (DMF) mit Benzol-, p-Toluol-und Naphthalinsulfochlorid im Molverhältnis 21 ergibt in einer Zweistufenreaktion isolierbare Tetramethyl-formamidinium-arylsulfonate. Auch bei der Reaktion im Molverhältnis 11 entstehen diese Produkte, nur bei p-Toluolsulfochlorid p-Toe p-Toluolsulfonsäure-N,N-dimethylamid isoliert. p-Toluolsulfonsäure gibt mitDMF und P₂O₅ ebenfalls das Formamidinium-sulfonat, während Naphthalin-1-sulfonsäure dasDMF protoniert und so zur entsprechenden Oniumverbindung führt.

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Reactions with dimethyl formamide, III: Reaction of arylsulfonyl chlorides and arylsulfonic acids with dimethyl formamide

The reaction ofDMF with benzene-, p-toluene-, and 1-naphthalenesulfonyl chloride in the molar ratio 21 formes isolable tetramethyl-formamidinium arylsulfonates in two steps. These products are also formed with a molar ratio 11, only p-toluenesulfonyl chloride results in p-toluenesulfonic N,N-dimethylamide. p-Toluenesulfonic acid too, reacts withDMF and P₂O₅ to the formamidinium sulfonate, whereas 1-naphthalenesulfonic acid protonates theDMF thus forming the corresponding onium compound.

     

Prins-Reaktionen mit Arylaldehyden, 3. Mitt.

By reaction of excess benzaldehyde with cyclohexene in presence of sulfuric acid besider-2,c-4-diphenyl-(t-4aH,c-8aH)-hexahydro-4H-1,3-benzodioxin (2) andr-4-phenyl-(t-4aH,c-8aH)-hexahydro-4H-1,3,2-benzodioxathiin-2,2-dioxide (3),trans-2-benzyloxycyclohexyl phenyl ketone (5) and (E)-3-benzylidene-1-cyclohexenyl phenyl ketone (6) are obtained. The formation of5 and6 is shown to proceed via an acid catalyzedCannizzaro reaction of benzaldehyde.

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2. Mitt.:H. Griengl undK. P. Geppert, Mh. Chem.107, 675 (1976).     

Floating spherical gaussian orbital model study of some organometallic systems. I. LiCH3, HBeCH3, and CH3BeCH3

The floating spherical Gaussian orbital method has been used to study the equilibrium geometries and electronic structures of some organometallic systems like LiCH₃, HBeCH₃, and CH₃BeCH₃. The predicted geometries are in good agreement with other theoretical estimates and available experimental results. Electron transfer values from carbon to metal atom and bond energies of Li? C and Be? C bonds are estimated and discussed. The wave functions obtained here have also been used to predict the electron momentum distributions and Compton profiles for LiCH₃, HBeCH₃, and CH₃BeCH₃.     

Synthesis of novel 1-phenyl-1H-indole-2-carboxylic acids. II. Preparation of 3-dialkylamino, 3-alkylthio, 3-alkylsulfinyl,and 3-alkylsulfonyl derivatives

The synthesis of novel indole-2-carboxylic acids with amino- and sulfur-containing substituents in the indole 3-position is described. An Ullmann reaction with bromobenzene converted 1H-indoles with 3-(acetylamino)- and 3-(diethylamino)-substituents into 1-phenyl-1H-indoles. Reaction of 3-unsubstituted indoles with thionyl chloride provided indole 3-sulfinyl chlorides, which reacted with alkyl and aryl Grignard reagents to form the corresponding sulfoxides. The indole sulfoxides thus obtained were reduced to sulfides or oxidized to sulfones.     

Cationic polymerization with boron halides. VI. Polymerization of styrene with BF3, BCl3, and BBr3

The polymerization of styrene with BF₃, BCI₃, and BBr₃ coinitiators and CH₂Cl₂ solvent has been investigated. The effects of temperature, monomer concentration, and the nature of the boron halide on molecular weights, molecular weight distribution, and conversion were determined. Molecular weights were found to decrease in the order BCl₃ >BF₃ >BBr₃. This sequence was discussed in terms of system ionicity and counterion stability. The overall energies of activation for polymerization (ΔE) were ?1.6 ± 0.3, ?1.9 ± 0.8, and ?0.9 ± 0.5 kcal/mole for BF₃, BCI₃, and BBr₃, respectively, which indicated similar overall polymerization mechanisms in the range of ?20 to ?80°C. The predominant molecular-weight-governing event in polymerizations with BCl₃, and BBr₃ was chain transfer to monomer, whereas with BF₃ chain transfer and termination were nearly equal. Chain termination in BCl₃-coinitiated polymerizations involves chlorination of the growing polystyryl cation by BCl₃OH^? and leads to benzylic chlorine termini.     

Zur Chemie der Selen-Stickstoffverbindungen, 3. Mitt.

Zusammenfassung Darstellung und Eigenschaften von Silber- und Kaliumsalzen der Imido-diselensäure werden beschrieben; Infrarot-Spektren sowieDebye-Scherrer-Diagramme dieser erstmalig dargestellten Verbindungen werden zu ihrer Charakterisierung mitgeteilt.Mit 2 Abbildungen     

Synthese von heterocyclen. V. 1, 3, 4-thiadiazol-2 (3 H)-one

A new and highly versatile method for the synthesis of 1, 3, 4-thiadiazol-2 (3 H)ones 1 is described. Methoxy-1,3,4-thiadiazoles- 5 , which are readily available by condensation of O-methyl thiocarbazate ( 2 ) with acid derivatives 3 , undergo an efficient cleavage to 1 and methyl chloride with hydrochloric acid in an anhydrous medium. Many new 5-substituted thiadiazolones, unavailable by earlier routes, were synthesized. Preparative as well as mechanistic aspects are discussed. With the aid of ¹³C-NMR. spectroscopy, the tautomerism of 1 was studied, and the tautomeric equilibria was shown to be dependent on the nature of the substituent in the 5-position. The thiadiazolones 1 exist predominantly in the oxo form. The percentage of the hydroxy form, however, increases with strongly electron withdrawing substituents in the 5-position. A good correlation with pK^a? and σ-values was observed.     

New synthesis of 2',3'-didehydro-2',3'-dideoxynucleosides.

The 3'-iodonucleoside 4 and the 3'-O-methylsulfonylthymidine 9 have been synthesized by condensation of silylated uracils 2 with methyl 5-O-tert-butyldiphensilyl-2,3-dideoxy-3-iodo-D-threo-pentofuran oside (3) and methyl 5-O-tert-butyldiphenylsilyl-2-deoxy-3-methylsulfonyl-D-erythro- pentofuranoside (8), respectively. The nucleoside 4 and 9 produced the corresponding 2',3'-didehydro-2',3'-dideoxynucleosides 5 in an elimination reaction on treatment with sodium methoxide. The compounds 5b showed no antiviral activity against HIV-1.     

Synthesen mit Nitrilen, 3. Mitt

Zusammenfassung Über das Disulfonsäurechlorid gelingt es, Disulfonsäureanilide des 5,7,12,14-Tetrahydropentacen-1,4; 6,13; 8,11-trichinons aufzubauen, welche als Indikatoren von Bedeutung sind. Weiters wird über die Reaktionen dieses Trichinons mit Cyanessigsäure berichtet.Herrn Prof. Dr.A. Zinke in Verehrung zum 70. Geburtstag gewidmet.