Protolytic reactions of 3,3'-dimethylnaphthidine and 3,3'-dimethoxybenzidine

The dissociation constants of diprotonated 3,3'-dimethylnaphthidine (DMN) and 3,3'-dimethoxybenzidine (DMB) have been determined spectrophotometrically. They are: pK(a1) = 2.62 +/- 0.03, pK(a2) = 3.33 +/- 0.09 for DMN: pK(a1) = 2.83 +/- 0.07, pK(a2) = 4.05 +/- 0.12 for DMB. The molar absorptivities (l.mole(-1).cm(-1)) of all forms of the indicators have been also determined: epsilon(B) = 1.68 x 10(4), epsilon(BH(+)) = 9.34 x 10(3), epsilon(BH(2+)(2)) = 1.80 x 10(3) at 300 nm for DMB; epsilon(B) = 7.33 x 10(3), epsilon(BH(+)) = 3.73 x 10(3), epsilon(BH(2+)(2)) = 0 at 330 nm for DMN.     

HYDROXYSTILBAZOLES AND HYDROXYAZAPHENANTHRENES: PHOTOCYCLIZATION AND FLUORESCENCE STUDIES

Abstract— As models for novel fluorescent probes, we have synthesized three isomeric hydroxystilbazole systems (4′-hydroxy-substituted 2-, 3-, and 4-stiIbazoles), examined their photocyclization-oxi-dation to four hydroxyazaphenanthrene systems, and made a preliminary study of their absorption and fluorescence spectra. All three stilbazoles can be prepared easily by addition of the isomeric picoline anions to 4-methoxybenzaldehyde, followed by dehydration and deprotection. Photocyclization proceeds efficiently, furnishing a single product isomer from each of the 2- and 4-stilbazole systems, and two isomeric azaphenanthrenes from the 3-stilbazole. The stilbazoles all have intense UV absorbance bands whose maxima depend upon solvent and pH; all three isomers have relatively similar spectra under neutral conditions and all three show a large red shift in base; in acid, however, the 2-and 4-stilbazole isomers show a greater red shift than the 3-stilbazole. The fluorescence of the stilbazoles is also solvent dependent, shifting to the red in more polar medium; red shifts are also observed in acid and base, but in acid, the 3-stilbazole shows a larger shift. The azaphenanthrene photocyclization products show absorbance spectra typical for quinolines and isoquinolines; their absorptivities are less than the stilbazoles, but their fluorescence is more intense. In general, the benzoquinolines have longer wavelength but weaker fluorescence than the benzoisoquinolines. Also, those isomers in which the resonance effects of the hydroxy and nitrogen groups can reinforce one another show longer wavelength emissions of greater intensity. All seven systems show dual fluorescence in water under neutral conditions, suggesting the emission from both non-ionized and ionized species in the excited state. In one case, the benzoisoquinoline system derived from 4′-hydroxy-4-stilbazole, an emission at 640 nm, observed in water over a wide pH range, is ascribed to a zwitterionic phototautomer. These stilbazoles, benzoquinolines and benzoisoquinolines may prove to be useful spectroscopic probes.     

Five-membered-ring-substituted 1-methyl-1H-indeno[1,2-b]pyridines

1-Methyl-1H-indeno[1,2-b]pyridine and 1-methyl-1H-5-(, -dicarbomethoxyvinyl)-(formyl, acetyl)indeno[3,2-b]pyridines were obtained by treatment of N-methyl-4-azafluorenium iodide, as well as mixtures of it with acetylenedicarboxylic ester, dimethylformamide (DMF), and phosphorus oxychloride or acetic anhydride, with bases. 4-Azafluoronenone was used to synthesize 9-(p-methoxyphenyl)-4-azafluoren-9-ol, which was reduced to 9-(p-methoxyphenyl)-4-azafluorene, and 1-methyl-1H-5-(p-methoxyphenyl)indeno[3,2-b]pyridine was obtained from the methiodide of the latter.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 10, pp. 1382–1386, October, 1981.     

The determination of traces of ammonium-nitrogen in aqueous solution by optical emission spectrometry with a high-frequency inductively coupled argon plasma source

A method for the determination of low levels of ammonium ion in solution by optical emission spectrometry with an inductively coupled argon plasma source operated at 27 MHz is presented. The ammonium ion is oxidized with sodium hypobromite in alkaline medium, the evolved nitrogen is passed into the argon plasma, and the NH emission intensity produced in the plasma at 336.0 nm is monitored. A practical detection limit of 0.1 μg N ml^-1 for 5-ml aqueous sample solutions has been obtained. The method has been applied to the determination of the exchangeable ammonium content of soil samples.     

The isotropy of Gaussian molecular networks and the stress-birefringence relations for rubberlike materials cross-linked in stressed states

Summary Using the model and some results of theJames andGuth theory of rabberlike elasticity, the relations between stress, birefringence, and strain (measured from the unstressed state) are re-derived by an argument which does not make use of certain assumptions used in previous derivations concerning the isotropy of the distribution of vectors joining junction mean positions and the fixing of junctions in their mean positions. It is proved that in the Gaussian approximation a rubberlike material is necessarily isotropic in the sense that the relations between the stress, strain, and refractive index involve no anisotropic constant tensors. The argument is applicable to networks whose junctions are introduced when the material is in different states of stress, and furnishes strong reasons for regarding the relations between flow birefringence and stress, previously derived on the basis of a network theory for concentrated polymer solutions, as being no longer restricted to solutions of constant viscosity.

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Zusammenfassung Unter Verwendung des Modells und einiger Ergebnisse der Theorie vonJames undGuth für Gummielastizit?t wurden die Beziehungen zwischen Spannung Doppelbrechung und Verformung (gemessen gegen den unbelasteten Zustand) erneut abgeleitet. Es wurde kein Gebrauch gemacht von den in früheren Ableitungen enthaltenen Annahmen über die Fixierung der Bindungen in mittleren Positionen und über die Isotropie der Verteilung der Vektoren, die diese Positionen verbinden. Es wird gezeigt, da? in derGauss-N?herung eines gummiartigen Materials Isotropie in dem Sinne erforderlich ist, da? die Beziehungen zwischen Spannung, Verformung und Brechungsindex keine anisotropen Tensoren der Konstanten enthalten. Diese Ableitung ist anwendbar auf Netzwerke, deren Bindungen eingeführt werden, w?hrend das Material in verschiedenen Spannungszust?nden vorliegt, und liefert eine gute Grundlage für die Annahme, da? die Beziehungen zwischen Str?mungsdoppelbrechung und Spannung, die früher auf Grund der Netzwerktheorie für konzentrierte Polymerenl?sungen abgeleitet wurden, nicht mehr auf L?sungen konstanter Viskosit?t beschr?nkt sind.

     

Synthesis of derivatives of pyrido[2,3-d]pyrimidines condensed with tetrahydropyran and tetrahydrothiopyran

Methods have been developed for obtaining derivatives of W-amino(oxo)-, 8,10-dioxo-, and 10-amino-8-oxo(thio)pyrano(thiopyrano) [4,3:4,5]pyrido[2,3-d]pyrimidine on the basis of 3-amino(benzylamino)-4-cyano (carbamoyl)pyrano(thiopyrano)[3,4-c]-pyridines.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 12, pp. 1683–1687, December, 1993.     

New approach to the synthesis of 3-amino-1,2-benzothiazine 1,1-dioxides

The possibility of obtaining 3-amino-1,2-benzothiazine 1,1-dioxides by nucleophilic substitution of the chlorine atom in 5-nitro-2-chlorobenzenesulfonamides by carbanions generated from substituted acetonitriles was studied.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 2, pp. 264–266, February, 1992.