Stereochemistry of planarchiral compounds,part X

2,7-Dibromo-1,6-methano[10]anulene (3) and 2,9-Dibromo-syn-1,6:8,13-diimino[14]anulene (9) were quantitatively separated into their enantiomers by chromatography on triacetylcellulose (TAC) in ethanol. X-ray structure analysis (Bijvoet technique) established the chiralities (+)(R)-3 and (+)(S)-9 for the dextrorotatory enantiomers.Comparison of the CD spectra allowed the configurational assignment to further optically active [10] and [14] anulenes which were also accessible by chromatography onTAC. Conversion of (+)(R)-2-bromo-1,6-methano[10]anulene (2) into the corresponding methylester (–)-4 confirmed its previously proposed chirality (–)(R).2,7-Dibromo-1,6-oxido[10]anulene (7) and 2,9-dibromo-syn-diimino[14]anulene (9) are in contrast to the 2,9-dibromo-syn-dioxido[14]anulene (10) optically stable until 250°C. Consequently their inversion barriers are higher than 42 kcal (176 kJ) mol^–1.The CD spectra of mono and disubstituted anulenes (with C₁ and C₂ symmetry, resp.) are compared: For the [10]anulenes theCotton effect around 330 nm seems to be specific for their configuration with a positive effect indicating (S)-chirality and vice versa. Some regularities concerning the chromatographic resolutions are discussed.

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Stereochemie planar chialer Verbindungen, 10. Mitt.: Röntgenkristallstruktur und absolute Chiralität überbrückter [10]- und [14] Anulene

Zusammenfassung 2,7-Dibrom-1,6-methano[10]anulen (3) und 2,9-Dibrom-syn-1,6:8,13-diimino[14]anulen (9) wurden durch Chromatographie an Triacetylcellulose (TAC) in Ethanol quantitativ in ihre Enantiomeren getrennt. Röntgenstruktur-analyse (Bijvoet-Technik) bewies für die rechtsdrehenden Enantiomeren die Chiralität (+)(R)-3 bzw. (+)(S)-9.Ein Vergleich der CD-Spektren ermöglichte die Konfigurationszuordnung weiterer optisch aktiver [10]- und [14]Anulene, die gleichfalls durch Chromato-graphie anTAC erhalten worden waren. Umwandlung von (+)(R)-2-Brom-1,6-methano[10]anulen (2) in den entsprechenden Methylester (–)-4 bestätigte dessen schon früher vorgeschlagene Chiralität (–)(R).Dibrom-1,6-oxido[10]anulen (7) und Dibrom-diimino[14]anulen (9) sind im Gegensatz zum Dioxido[14]anulen (10) bis 250°C optisch stabil. Ihre Inver-sionsbarrieren liegen somit über 42 kcal (176kJ) mol^–1.Die CD-Spektren von mono- und disubstituierten Anulenen (mit C₁ bzw. C₂-Symmetrie) werden verglichen: Für die [10]Anulene scheint derCottoneffekt um 330 nm konfigurationsspezifisch zu sein, wobei ein positiver Effekt (S)-Chiralität anzeigt — und vice versa. Einige Regelmäßigkeiten bezüglich der chromatographischen Enantiomerentrennung werden diskutiert.

     

Inclusion complexes of proteins: Interaction of cyclodextrins with peptides containing aromatic amino acids studied by competitive spectrophotometry

The stability constants were measured of inclusion complexes formed from aromatic amino acids and their oligopeptides with - and-cyclodextrin, hydroxypropyl-cyclodextrin, and partially methylated-cyclodextrin. The method of competitive spectrophotometry withp-nitrophenol as a competing reagent was used, and measurements were made at pH 7.4-Cyclodextrin formed complexes of higher stability than the other hosts. The stability of complexes of oligopeptides containing L-phenylalanine was invariably higher than that of L-phenylalanine itself. A model for interaction of proteins with cyclodextrins is proposed, in which the most stable complexes are formed when the native functional form of proteins is unfolded and the nonpolar residues that are buried inside the structure are exposed to water. The complexation of the unfolded structure favors its formation; thus thermal denaturation of proteins is easier in the presence of cyclodextrins. On the other hand, this complexation prevents the intermolecular association of unfolded structures by noncovalent hydrophobic bonding between the exposed nonpolar residues; furthermore, the unfolded complexed forms may revert to the native functional form. This prevention of intermolecular association may explain the stabilizing effect of cyclodextrins on solutions of proteins: a return to the native form is achieved more easily from the complexed, unfolded form than from the unfolded, aggregated forms.Dedicated to Professor József Szejtli.     

Aromastoffe der roten Passionsfrucht. Zwei neue Edulanderivate

Aroma Constituents of the Purple Passion Fruit. Two New Edulan Derivatives The isolation of (2R*, 4S*, 4aS*, 8aS*)-4,4a-epoxy-4,4a-dihydroedulan ( 1 ), and (2R*, 3S*, 8aS*)-3-hydroxyedulan ( 2 ), two new constituents of the purple passion-fruit (Passiflora edulis SIMS ), is reported. Racemic epoxide 1 was synthesized by oxidation of edulan 6 with peracidic acid, and racemate of alcohol 2 was obtained by reduction of ketone 7 , one of the chromic acid oxidation-products of edulan 6 .     

Fluorénacènes et fluorénaphènes Synthèses dans la série des indéno-fluorènes,XV [1] Méthyl-5-dihydro-10, 12-indéno [2, 1-b]fluorène

Starting from α-methylchalcone and diethyl ketone the title compound, II, has been synthesized in 6 steps (overall yield 26%). As an intermediate compound the gold yellow 10, 12-dioxoderivative of II was also obtained.     

Effects of inductive substituents on electronic spectra aza analogs of fluoranthene

The conditions under which the Hückel molecular orbital (HMO) treatment of inductive substituent effects can be expected to be reliable are discussed from the viewpoint of the Pariser-Parr-Pople (PPP) model. The HMO theory fails to predict correctly the direction of the shift of the first intense band in the ultraviolet spectrum of fluoranthene (1–1 transition) on 3-aza substitution. Calculations on the five azafluoranthenes using the simple version of the PPP method suggest that this is due to strong mixing of hydrocarbon states by the effect of the substituent and predict significant changes in energies, intensities, and polarizations of fluoranthene electronic transitions on aza substitution. Transition moment directions derived from dichroic absorption of 3-azafluoranthene in stretched polyethylene sheets are in agreement with PPP predictions. Arguments are given against a previous assignment of the first transition in 1-azafluoranthene as n- ^*.

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Zusammenfassung Aus der Sicht des Pariser-Parr-Pople-Modells (PPP) werden die Bedingungen diskutiert, unter denen die HMO-Behandlung induktiver Substituenteneffekte als zuverlässig erscheint. Die HMO-Theorie ist nicht in der Lage, die Verschiebung der ersten intensiven Bande im UV-Spektrum des Fluoranthens (1–1-Übergang) bei 3-Aza-Substitution richtig vorauszusagen. Berechnungen an den 5 Azafluoranthenen nach der einfachen PPP-Methode lassen vermuten, daß diese Tatsache durch eine starke Vermischung von Kohlenwasserstoffzuständen — hervorgerufen durch die Wirkung des Substituenten — bedingt ist. Die PPP-Methode sagt ferner beträchtliche Änderungen in den Energien, Intensitäten und Polarisationen der Elektronenübergänge des Fluoranthens voraus, wenn man im Fluoranthen eine Aza-Substitution vornimmt. Die Richtungen des Übergangsmoments, die aus der dichroitischen Absorption des 3-Azafluoranthens in langgestreckten Polyäthylenschichten abgeleitet werden können, stimmen mit den Voraussagen von PPP-Berechnungen überein. Es werden Argumente vorgebracht, die gegen eine Kennzeichnung des ersten Übergangs in 1-Azafluoranthen als n- ^*-Übergang sprechen.

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Résumé On discute à l'aide du modèle de Pariser-Parr-Pople (PPP) les conditions de validité du traitement par la méthode de Hückel (HMO) des effets de substituants inductifs. La méthode de Hückel ne peut prédire correctement la direction du déplacement de la première bande intense du spectre UV du fluoranthène (dite transition «1–1») dans les substitutions aza en 3. Les calculs sur 5 azafluoranthènes à l'aide de la méthode PPP ordinaire suggèrent que cet échec est du à un fort mélange des états de l'hydrocarbure sous l'effet du substituant, et prédit des changements importants dans les énergies, les intensités et les polarisations des transitions du fluoranthène par les substitutions aza. Les directions des moments de transition déduits de l'absorption dichroïque du 3 aza fluoranthène dans des feuilles de polyéthylène étiré sont en accord avec le calcul PPP. On apporte des objections à la caracterisation antérieure de la 1 ère bande du 2 azafluoranthène comme une bande n- ^*.

     

Jodometrische Bestimmung von Antimon in Erzen

Zusammenfassung In komplizierten Erzmaterialien wird Antimon mit Hilfe des Freiberger Aufschlusses in Lösung gebracht und von vielen Begleitelementen getrennt. Die Sulfosalze werden mit Wasserstoffperoxid oxydiert und Sb^v danach mit Sulfit zu Sb^III reduziert. Nach Zugabe von Weinsäure und ÄDTA wird Sb bei p_H 9 mit Natriumdiäthyldithiocarbamidat gefällt und mit Chloroform extrahiert. Aus der organischen Phase wird Antimon(III) mit Cadmium verdrängt, rückextrahiert und in der wäßrigen Phase mit einer Jod-Maßlösung titriert.

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Summary For the determination of antimony in complicated ores the sample is fused with potassium carbonate and sulphur. In this way a separation from many accompanying elements is achieved. The thiosalts are oxidized by hydrogen peroxide, whereupon antimony is reduced from the quin quevalent to the trivalent state by means of sodium sulphite. After addition of tartaric acid and EDTA antimony is precipitated at p_H 9 with sodium diethyldithiocarbamidate and extracted with chloroform. From the organic phase antimony is reextracted by displacement with cadmium salt and titrated with a standard iodine solution.

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Ein ähnliches Verfahren zur Zinkbestimmung vgl. Jankvoský, J.: diese Z. 201, 330 (1964).     

High thermodynamic stability and extraordinary kinetic inertness of copper(II) complexes with 1,4,8,11-tetraazacyclotetradecane-1,8-bis(methylphosphonic acid): example of a rare isomerism between kinetically inert penta- and hexacoordinated copper(II) complexes

In an aqueous solution at room temperature, 1,4,8,11-tetraazacyclotetradecane-1,8-bis(methylphosphonic acid) (H(4)L(1)) and Cu(I) (I) form a pentacoordinated (pc) complex, pc-[Cu(L(1))](2-), exhibiting conformation I of the cyclam ring. At high temperature, the complex isomerises to a hexacoordinated isomer, trans-O,O-[Cu(L(1))](2-), with a trans-III conformation of the cyclam ring. In pc-[Cu(L(1))](2-), four ring nitrogen atoms and one phosphonate oxygen atom are arranged around Cu(I) (I) in a structure that is half-way between a trigonal bipyramid and a tetragonal pyramid, with one phosphonic acid group uncoordinated. In the trans-O,O-[Cu(L(1))](2-) isomer, the nitrogen atoms form a plane and the phosphonic acid groups are in a mutually trans configuration. A structurally very similar ligand, 4-methyl-1,4,8,11-tetraazacyclotetradecane-1,8-bis(methylphosphonic acid) (H(4)L(2)), forms an analogous pentacoordinated complex, pc-[Cu(L(2))](2-), at room temperature. However, the complex does not isomerise to the octahedral complex analogous to trans-O,O-[Cu(L(1))](2-). Because of the high thermodynamic stability of pc-[Cu(L(1))](2-), (logbeta=25.40(4), 25 degrees C, I=0.1 mol dm(-3) KNO(3)) and the formation of protonated species, Cu(I) (I) is fully complexed in acidic solution (-log [H(+)] approximately 3). Acid-assisted decomplexation of both of the isomers of [Cu(H(2)L(1))] takes place only after protonation of both uncoordinated oxygen atoms of each phosphonate moiety and at least one nitrogen atom of the cycle. The exceptional kinetic inertness of both isomers is illustrated by their half-lives tau(1/2)=19.7 min for pc-[Cu(H(2)L(1))] and tau(1/2) about seven months for trans-O,O-[Cu(H(2)L(1))] for decomplexation in 5 M HClO(4) at 25 degrees C. The mechanism of formation of pc-[Cu(L(1))](2-) is similar to those observed for other macrocyclic complexes.     

Fundamental Aspects of Ionic Dissociations: The Fragmentation Pathways of Excited Bicyclobutane Cations

A most recently developed method to quantify the fragmentation pathways of excited radical cations is presented. Using bicyclobutane cation as an illustrative example, the RRKM analysis of the breakdown diagram determined by He-Iα photoelectron-photoion coincidence spectroscopy is outlined. The results imply complete isomerization to 1,3-butadiene cation preceding the dissociative processes. The rate-energy functions of four competitive primary fragmentation reactions, leading to C₃H, C₄H, C₄H and C₂H are established. There is compelling evidence that the production of C₂H fragment ions does not compete effectively with these four reactions. The extent of kinetic and competitive shift effects is determined. The derived enthalpies of formation are in excellent accord with the available high quality reference data. The relative importance of different fragmentation pathways which ultimately lead to fragment ions of identical mass to charge ratio is assessed.     

Concrete quantum logics with covering properties

LetL be a concrete (=set-representable) quantum logic. Letn be a natural number (or, more generally, a cardinal). We say thatL admits intrinsic coverings of the ordern, and writeL C _n , if for any pairA, BL we can find a collection {C _i iI}, where cardI<n andC _i L for anyiI, such thatA B= _il C _i . Thus, in a certain sense, ifLC _n , then the rate of noncompatibility of an arbitrary pairA,BL is less than a given numbern. In this paper we first consider general and combinatorial properties of logics ofC _n and exhibit typical examples. In particular, for a givenn we construct examples ofL C _n+1\C _n . Further, we discuss the relation of the classesC _n to other classes of logics important within the quantum theories (e.g., we discover the interesting relation to the class of logics which have an abundance of Jauch-Piron states). We then consider conditions on which a class of concrete logics reduce to Boolean algebras. We conclude with some open questions.