The Derivation of Inductive Substituent Constants from pKa Values of 4-Substituted Quinuclidines. Polar effects. Part I

Thermodynamic pK_a-values have been determined for 38 4-substituted quinuclidinium perchlorates. They are remarkably sensitive to the polar effect of the substituent and cover a range of 3.63 pK_a units. Furthermore, they vary linearly and almost equally with temperature since the contribution of the TΔS° term to the free energy of ionization is relatively small and constant. The magnitude of the polar effect of the 4-cyano group varies with the solvent and appears to depend on its ability to form hydrogen bonds to the substituent rather than its dielectric constant. New inductive substituent constants σ_I^q are derived from the pK_a values. Their correlation with known inductive constants is only fair or unsatisfactory, especially as regards the relative order of hydrogen and the alkyl groups. The discrepancies can be ascribed mainly to the different models used to derive the substituent constants.     

Cyclisierungsreaktionen zu Pyrano[3,2-c]pyridinen und pyrano[3,2-c]chinolinen unter Verwendung von Ethoxymethylen-malodinitril bzw.-cyanessigester Synthesen mit Nitrilen, 50. Mitt. pyrano[3,2-c]quinolines with ethoxymethylene-malonitrile and-ethyl cyanoacetate,resp.

Reaction of ethoxymethylene-malonitrile and ethoxymethyleneethyl cyanoacetate, resp., with 4-hydroxy-2-pyridones (1a–b) and 4-hydroxy-2-quinolones (3a–b) leads to 2,5-dioxo-5,6-dihydro-2 H-pyrano[3,2-c]pyridine-(2a–d) and 2,5-dioxo-5,6-dihydro-pyrano[3.2-c]quinoline-derivatives (4a–d), resp.2a–d and4a–d exhibit remarkable visible fluorescence. Absorption- and emmission-data in different solvents are reported.     

Zur Verwendung von Quecksilber(I)-nitrat als reduktometrisches Reagens

Ohne ZusammenfassungVgl. diese Z. 137, 129 (1952/53); 138, 118 (1953)     

Herstellung keramischer Pulver. II. Über die Bildung von Mg2TiO4, MgTiO3 und MgTi2O5 durch Hydrolyse von 2-Ethoxyethylaten

Preparation of Ceramic Powders. II. Mg₂TiO₄, MgTiO₃, and MgTi₂O₅ Formed by Hydrolysis of 2-Ethoxyethylates Solutions of 2-ethoxyethylates of magnesium and titanium in 2-ethoxyethanol submitted to hydrolysis, evaporation and heating of the residue up to 450°C allow to prepare Mg₂TiO₄, MgTiO₃, and MgTi₂O₅ in an amorphous state with smaller than 1% of volatile components. Highly dispersed powders showing an increased sintering activity are obtained as a result of recrystallization. Mg₂TiO₄ is formed as inverse spinel phase in a metastable state.     

Polar Substituent Effects in the Solvolysis of Primary and Tertiary Alkyl Halides. Polar Effect IX

When the Hammett-Taft equation log (k/k_o)=ρ^q · σ is applied to the solvolysis of the 3-substituted propyl bromides 6a-6i in ethanol/water 4:1 (v/v) log k correlates linearly with σ except in cases where R exerts an anchimeric effect. The reaction constant ρ^q for 6 is ? 0.12 and is typical for a nucleophilic solvent-assisted k_s process at a primary C-atom. The tertiary halides 1 and 3 , however, which react with little or no nucleophilic solvent assistance, i.e. by k_c processes, lead to larger ρ^q values of ?0.71 and ?1.14, respectively. The reaction constant p^q is therefore a sensitive gauge for charge development in the transition state for solvolysis of saturated compounds.     

Photocycloaddition of Cyclohex‐2‐enones to Penta‐1,2,4‐triene

Dihydrothiinone 9a undergoes photocycloaddition regioselectively to all three C?C bonds of penta‐1,2,4‐triene ( 10 ), the relative stabilities of the biradical intermediates determining the product distribution. In contrast, cyclohexenone 9b and dihydropyranone 9c afford more complex mixtures of bicyclo[4.2.0]octanones, which also turn out to be less stable on chromatographic workup, reflecting the higher strain due to the shorter bond lengths (C? O and C? C vs. C? S) in the six‐membered rings, respectively.     

Inverse Pulspolarographie am h?ngenden Quecksilbertropfen

Zusammenfassung Die inverse Voltammetrie am hängenden Quecksilbertropfen mit pulspolarographischer Aufzeichnung der anodischen Auflösungsströme wird auf ihre Leistungsfähigkeit untersucht. 10^–9 M Lösungen von Cu, Pb, Cd, Zn können im Routinebetrieb analysiert werden. In Alkalisalzmatrices sind Direktbestimmungen der Schwermetalle im 10^–7 bis 10^–8%-Bereich möglich. Die Nachweisgrenze für Cd beträgt 5 · 10^–11 Mol/l. Die Empfindlichkeit der Methode wird mit derjenigen verwandter voltammetrischer Verfahren verglichen.

---

Anodic stripping pulse polarography at the hanging mercury drop electrodeDetermination of Cu, Pb, Cd and Zn

The efficiency of anodic stripping pulse polarography at the H.M.D.E. is tested. In routine work the analysis of 10^–9 M solutions of Cu, Pb, Cd, Zn offers no difficulty. The determination of the elements in alkali salts in the 10^–7 to 10^–8% range is possible. The detection limit for Cd was found to be 5×10^–11 M. The sensitivity of the method was compared with those of related voltammetric techniques.

     

Synthesen mit Nitrilen, 29. Mitt.: Die linearen Kondensationsprodukte aus Dimethylaminophenylpropenon und Malonsäuredinitril

Zusammenfassung In unpolaren Lösungsmitteln kondensieren sich monomeres und dimeres Malonitril mit Dimethylamino-phenyl-propenon zu linearen Dienen bzw. Trienen. 2-Cyan-5-dimethylamino-3-phenyl-2,4-pentadienamid (4) kann als Zwischenprodukt für die Bildung von Pyridonen aus Enaminoketonen und Cyanacetamid aufgefaßt werden, da in saurem Medium die Cyclisierung zum 2-Oxo-4-phenyl-1,2-dihydro-pyridin-3-carbonitril bzw. dem Carbonsäureamid gelingt.

---

Syntheses with nitriles, XXIX: The linear condensation products from dimethylaminophenyl propenone with malononitrile

Monomeric and dimeric malononitrile condense in nonpolar solvents with dimethylamino phenyl propenone to form linear dienes and trienes, resp. 2-Cyano-5-dimethylamino-3-phenyl-2,4-pentadienamide (4) represents an intermediate in the formation of pyridones from enamine ketones and cyanoacetamide. It is cyclised in acidic medium to 2-oxo-4-phenyl-1,2-dihydropyridine-3-carbonitrile (8) (or-3-carboxamide,9).

---

---

Herrn Prof.O. Hromatka zum 65. Geburtstag gewidmet.