Synthesen von Heterocyclen, 122. Mitt.: Über die Reaktion des Perimidons mit aktiven Malonestern

Zusammenfassung Perimidon (1) reagiert mit monosubstit. Malonsäure-trichlorphenylestern (2) bei 250° zu 9-Hydroxy-5,7-dioxo-4,5-dihydro-7H-pyrido[1,2,3-cd]perimidinen (3), die durch saure Hydrolyse zu 10-Amino-4-hydroxy-benzo[h]carbostyrilen (4) gespalten werden.

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Syntheses of heterocycles, CXXII: Reaction of perimidone with reactive malonates

Perimidone (1) reacts with monosubstituted 2.4.6-trichlorophenyl malonates at 250° to 9-hydroxy-5.7-dioxo-4.5-dihydro-7H-pyrido[1.2.3-cd]perimidines (3), which are cleaved by acid yielding 10-amino-4-hydroxy-benzo[h]quinolin-2-ones (4).

     

Adsorption of lignosulphonates on polystyrene latex particles from aqueous solution and flocculation of the dispersions by electrolytes

Summary The adsorption isotherms of lignosulphonates with various degrees of sulphonation (0.5, 1,0, 2.0 and 4.0 moles per 840 unit weight of lignin) were measured on polystyrene latex particles from aqueous solution at 25 °C. The results showed that the lignin with the lowest degree of sulphonation gave the highest adsorption. The lignin with 1.0 and 2.0 degrees of sulphonation gave similar adsorption which was lower than that obtained with the half sulphonated lignin. However, further increase in degree of sulphonation resulted in an increase in the adsorption.Adsorption layer thickness measurements showed that the lignosulphonate with half degree of sulphonation gave thicker layers than that with 2.0 moles sulphonation. Increasing electrolyte (NaCl and CaCl,) concentration resulted in a decrease in the adsorbed layer thickness. Microelectrophoresis at 25 °C, showed only small differences in the zeta potential as a function of degree of sulphonation. Addition of electrolytes (KCl, Na₂SO₄ and CaCl₂) showed a reduction in the zeta potential. Flocculation by salts of various valence types, namely KCl, Na₂SO₄ and CaCl₂ showed that the critical flocculation concentration (C.F.C.) decreases in the order KCl > Na₂SO₄ > CaCl₂. The change in degree of sulphonation had only a marginal effect on the C.F.C.

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Zusammenfassung Die Isothermen der Adsorption von Lignosulfonaten mit verschiedenen Sulfonierungsgraden (S = 0,5, 1,0, 2,0 und 4,0 Mole pro 840 Gewichtseinheit des Lignins) an PolystyrolLatex-Teilchen in wäßriger Lösung wurden bei 25 °C gemessen. Hiernach wird Lignin mit den niedrigsten S-Werten am stärksten adsorbiert. Lignine mitS = 1,0 und 2,0 zeigen ähnliche Adsorption; sie ist aber kleiner als die fürS = 0,5. Mit weiter steigendemS nimmt die Adsorption zu.Aus der Messung der Dicke der Adsorptionsschicht folgt, daß fürS = 0,5 größer als fürS = 2,0 ist. Bei wachsendem Zusatz von NaCl oder CaCl₂ fällt ab. Nach Mikroelektrophorese-Messungen bei 25 °C hängt das -Potential nur wenig vonS ab. fällt durch die Gegenwart von KCl, Na₂SO₄ oder CaCl₂ ab. Mit den gleichen Salzen erfolgt eine Ausflockung, wobei die kritische Flockungskonzentration CFC in der Reihenfolge KCl, Na₂SO₄, CaCl₂ abnimmt; CFC ändert sich nur wenig mitS.

     

Massenspektrometrie isomerer Diazaphenanthrene—I

The mass spectra of five diazaphenanthrenes formed by photochemical cyclodehydrogenation of styryl diazines are investigated. It is shown that fragmentation of these compounds starts almost exclusively at the heterocyclic part of the molecule and proceeds by competitive α-cleavage. From the intensity ratios of the ions [M ? H˙]⁺, [M ? HCN]⁺˙, [M ? N₂]⁺˙ and [M ? 2 HCN]⁺˙ generated in this way, each isomer can unequivocally be identified.     

On the average length of lexicographic paths

A bound is given for the average length of a lexicographic path, a definition that is motivated by degeneracies encountered when using the randomized simplex method.     

Alkylierung ambidenter Heterocyclen-Anionen, 1. Mitt.: Über die Benzylierung des 4-Hydroxy-carbostyrils

Zusammenfassung 4-Hydroxy-carbostyrile (1a–c) werden mit Benzylchlorid inDMF bevorzugt zu den 4-Benzyloxy-carbostyrilen (2a–c) alkyliert. In wäßr. NaOH dagegen erhält man aus1a und1c als Hauptprodukt das 3,3-Dibenzyl-2,4-dioxo-1,2,3,4-tetrahydrochinolin (3).

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Alkylation of 4-hydroxy-quinol-2-ones (1a–c) with benzyl chloride inDMF in the presence of K₂CO₃ mainly gives the 4-benzylethers2a–c. However, carbon dialkylation takes place in aqueous NaOH and the main product of the reaction between benzylchloride and1a is 3.3-dibenzyl-2.4-dioxo-1.2.3.4-tetrahydro-quinoline3.

     

Calcul théorique des énergies de divers arrangements géométriques de la molécule (η5-C5H5)2TiCl2

The molecular energy of the complex (η⁵-C₅H₅)₂TiCl₂ has been calculated for experimental geometry and for several hypothetical forms by a semi-empirical CNDO/2 approach. The energy difference between experimental (quasi-tetrahedral) geometry and a planar geometry is ca. 20 kcal mol^?1. This difference is sufficiently high to explain the difficulty of the inversion process.     

Zur reaktionsweise von triafulvenen mit azomethinyliden

The reaction of the azomethine ylides 2a–c with cyclopropenones 3 and of 2a with methylene cyclopropenes 7 leads via (3+3)-cycloaddition to pyridones-4 5 and 1,4 - dihydro - N - methyl - 4 - methylene - pyridines 8, respectively. The merocyanine systems 8 exhibit marked solvatochromic and thermochromic properties.     

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.

     

Analytical applications of crown ethers : III. Extraction and determination of nitrophenol isomers

The oxidation of aldehydes by dicyclohexyl-18-crown-6-potassium permangante complex is presented. Results obtained by this procedure showed that the presence of crown ether (DCC) and the catalyst play an important role in the oxidation of the aldehydes. The stoichiometry found corresponds to 2 μeq of permanganate per 1 μmol of aldehydes in all cases. Alcohols and ketones are not oxidized. Finally, a method for quantitative evaluation of aldehydes is proposed.