Phenazine, 3. Mitt.: N-(o-Aminophenyl)-benzo[a]phenazin-5-amin, das vermeintliche “Dihydronaphthodiphenazin”Kehrmanns, und seine Derivate

The dihydronaphthodiphenazine ofKehrmann, which is according toBadger andPettit reported to be 14-o-aminophenyl-13,14-dihydro-5,8,13,14-tetraaza-6,7-benzopentaphene, is N-(o-aminophenyl)-benzo[a]phenazin-5-amine. This was proved by chemical and spectroscopic investigations. The structures of the derivatives prepared byBadger andPettit are also corrected and the acetylation processes are cleared up.     

Neue stellungsisomere reineckesalzähnliche Verbindungen mit Toluidinen

Zusammenfassung Es wurden eine Reihe von Substitutionsreaktionen mit entwässertem K₃[Cr(NCS)₆] und aromatischen Aminen, ohne Verwendung von Lösungsmitteln, durchgeführt. Es wurde beobachtet, da die sehr schwachen Basen mit p_K-Werten 14–16, wie die isomeren Mono- und Dinitro-aniline, die Anthranil- und Sulfanilsäuren, für diese Substitutionsreaktionen ungeeignet sind. Die Alkyl-anilinderivate, wie daso-, m- undp-Toluidin (p_K=10–11) bilden dagegen leicht reineckesalzähnliche Verbindungen: Amin· H[Cr(Toluidin)₂(NCS)₄]. Die Zusammensetzung der neuen Komplexanionen wurde bei einer Reihe von doppelten Umsetzungsreaktionen mit den Chlorhydraten einiger heterocyclischen Aminen festgestellt.Für die Klärung einiger Strukturfragen wurden spektrophotometrische Untersuchungen im UV und IR durchgeführt und die thermische Stabilität bzw. der Mechanismus des Pyrolysenvorganges auf thermogravimetrischem Wege verfolgt.

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Substitution reactions of anhydrous K₃[Cr(NCS)₆] with aromatic amines without applying of solvents were studied.It was observed, that the very weak bases (pK-values 14–16, e.g. isomeric mono- and dinitro-anilines, the anthranilic and sulfanilic acids) are unsuitable for substitution reactions. The alkylaniline derivates e.g.o-, m- andp-toluidine (pK=10–11) form easily reineckesalt analogous compounds: Amin· ·H[Cr(toluidine)₂(NCS)₄]·The formula of the 3 new complex anions: [Cr(toluidine)₂ (NCS)₄]- was established by preparative methods, with a series of double decomposition reactions, using chlorohydrates of some heterocyclic amines for this purpose. From spectroscopical investigations (UV and IR) some structural problems are resolved and discussed.The thermal stability and the mechanism of pyrolysis of these salts was studied by thermogravimetric analysis.

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Mit 8 Abbildungen     

Chloryl nitrate: a novel product of the OClO + NO3 + M recombination

The products of the reaction of OClO with NO3 were investigated between 220 and 298 K using a flow reactor and infrared, visible, and ultraviolet analysis. At temperatures below 250 K new infrared and ultraviolet absorption features were observed and assigned to the novel compound chloryl nitrate (O2ClONO2). Additionally, ClO and NO2 were observed as reaction products, indicating the existence of a second reaction channel. O2ClONO2 formation predominates at temperatures below 230 K. The reaction rate constant at 220 K is estimated to be on the order of 10(-14) cm3 molecule-1 s-1 in 1-5 Torr of helium. These observations suggest that O2ClONO2 may exist in the terrestrial stratosphere.     

Angular momentum decoupling approximations in the quantum dynamics of reactive systems

Two methods for implementing angular momentum decoupling approximations in quantum mechanical reactive scattering examined. Applications of both reactive and nonreactive H + H₂ collisions indicate that for the most intense individual reactive transitions and for all degeneracy-averaged ones, these decoupling methods (especially the “proper” decoupling method) yield results in good agreement with those of fully-coupled calculations. However, for the less intense reactive transitions and all individual nonreactive transitions, very large errors can result from use of these approximate methods.     

Partial purification of active delta and epsilon subunits of the membrane ATPase from escherichia coli.

We have partially purified active delta and epsilon subunits of the E. coli membrane-bound Mg2+-ATPase (ECF1). Treating purified ECF1 with 50% pyridine precipitates the major subunits (alpha, beta, and gamma) of the enzyme, but the two minor subunits (delta and epsilon), which are present in relatively small amounts, remain in solution. The delta and epsilon subunits were then resolved from one another by anion exchange chromatography. The partially purified epsilon strongly inhibits the hydrolytic activity of ECF1. The epsilon fraction inhibits both the highly purified five-subunit ATPase and the enzyme deficient in the delta subunit. The latter result indicates that the delta subunit is not required for inhibition by epsilon. By contrast, two-subunit enzyme, consisting chiefly of the alpha and beta subunits, was insensitive to the ATPase inhibitor, suggesting that the gamma subunit may be required for inhibition by epsilon. The partially purified delta subunit restored the capacity of ATPase deficient in delta to recombine with ATPase-depleted membranes and to reconstitute ATP-dependent transhydrogenase. Previously we reported (Biochem, Biophys. Res. Commun. 62:764 [1975]) that a fraction containing both the delta and epsilon subunits of ECF1 restored the capacity of ATPase missing delta to recombine with depleted membranes and to function as a coupling factor in oxidative phosphorylation and for the energized transhydrogenase. These reconstitution experiments using isolated subunits provide rather substantial evidence that the delta subunit is essential for attaching the ATPase to the membrane and that the epsilon subunit has a regulatory function as an inhibitor of the ATPase activity of ECF1.     

Retention of85Sr and147Pm on insoluble hydroxides and phosphates prepared by the sol-gel procedure

Retention of strontium and promethium on hydroxides (hydrated oxides) and phosphates of iron and chromium prepared by the sol-gel method was studied. The sorption was determined under static conditions depending on the pH of the solution. The sorption isotherms and retention were investigated under dynamic conditions.     

Intramolecular "Aryl-metal chelate ring" pi,pi-interactions as structural evidence for metalloaromaticity in (aromatic alpha,alpha'-diimine)-copper(II) chelates: molecular and crystal structure of aqua(1,10-phenanthroline)(2-benzylmalonato)copper(II) three-hydrate

By reaction of Cu(2)CO(3)(OH)(2), 2-benzylmalonic acid (H(2)Bzmal), and 1,10-phenanthroline (phen), [Cu(Bzmal)(phen)(H(2)O)] x 3H(2)O (compound 1) has been obtained and characterized by thermal, spectral, magnetic, and X-ray diffraction methods. The molecular structure of 1 is remarkably similar to that of [Cu(Bzmal)(bipy)(H(2)O)] x 2H(2)O (compound 2, bipy = 2,2'-bipyridine). In both complexes, the aryl(Bzmal) ring produces an unexpected pi,pi-stacking interaction with the Cu(II)-(aromatic alpha,alpha'-diimine) chelate ring, at an average distance d(pi)(-)(pi) of 3.40 A, involving roughly parallel and smoothly slipped rings. This insight is discussed as new structural evidence for metalloaromaticity of Cu(II)-(aromatic alpha,alpha'-diimine) chelate rings. Interestingly, 1 recognizes itself by a weak intermolecular pi,pi-stacking interaction between aryl(Bzmal) ligands to give pairs of complex molecules. In contrast, there is an intermolecular pyridyl-pyridyl pi,pi-stacking interaction also forming pairs of complex molecules in 2.     

pH-metric studies on some ternary complexes of lanthanones

Stepwise mixed ligand complex formation has been cited for the formation of 111,Ln(III)—NTA—catechol ternary complexes potentiometrically [whereLn(III)=La(III), Pr(III) or Nd(III)]. The results of titration curves indicate the formation of 11,Ln(III)—NTA complexes in beginning and the addition of catechol, takes place later on in the higher buffer region. The relative stability of these ternary complexes in terms of metal ion has been reported as La(III)< 相似文献   

Biogenic substances in sediments and fossils

Most sedimentary rocks contain small concentrations of finely divided organic material. With the aid of modern analytical methods, samples of such rocks can be examined in detail, and conclusions can be drawn concerning the origin of the organic substances. Intact or modified biogenic compounds such as paraffins, isoprenoids, alcohols, ketones, carboxylic acids, steroids, triterpenes, and porphyrins have been isolated from the soluble fractions of the organic material of many sediments and from identified fossils of various geological ages. Even Precambrian rocks contain biogenic substances, so that life forms must have existed more than three billion years ago. The main component of the organic material is “kerogen”, the complicated polymeric structure of which has not yet been established.