Thermisches Verhalten von 1,2-Dipropenylbenzolen

1-cis, 2-cis-Dipropenylbenzene (cis, cis- 1 ) isomerises thermally at 215–235° with 1st order kinetics to give trans, cis- 1 and vice versa. At equilibrium 89% trans, cis- and 11% cis, cis- 1 are present. It is shown by thermal rearrangement of cis, cis-2′, 2″-d₂- 1 that the isomerisation is attributable to aromatic [1, 7a]-sigmatropic H-shifts. trans, trans- 1 rearranges thermally at 225–245° to yield 2, 3-dimethyl-1, 2-dihydronaphthalene ( 2 ). The formation of 2 can be visualized by disrotatory ring closure followed by an aromatic [1, 5s]-sigmatropic H-shift. 2 is also formed when, cis, cis- or trans, cis- 1 are heated for 153 h at 225°. Besides 2 a small amount (3%) of 1-ethyl-1, 2-dihydronaphthalene ( 5 ) is formed. The rearrangement of trans, trans- 1 and trans, trans-2′, 2″-d₂- 1 shows a secondary isotope effect k_H/k_D = 0,90.     

Thermisches Verhalten von Cyclopropa[c]chromenen

The Cyclopropa[c]chromenes 14 , trans-and cis- 15 , trans-and cis- 16 and 17 rearrange on heating > 200° in N, N-diethylaniline to give 2-alkyl-2H-chromenes 7, 8, 21, 22. The rate determining step of this rearrangement is the ‘homoelectrocyclic’ ring opening of the cyclopro-pa[c]chromenes to give ω-allyl-quinomethanes of type 4. These intermediates show fast [1,5s] and [1,7a] H-shifts, followed by electrocyclic ring closure. Deuterium labelling experiments are in agreement with this mechanism. The remarkable dependence of the rates of rearrangement with respect to the stereochemistry of the cyclopropa[c]chromenes (cf. table 2) suggests that in the first step only one of the two possible disrotatory modes of ring opening is involved.     

Thermisches Verhalten von 1-Acylbenzocyclobutenen; eine neue Isochromensynthese

1-Acyl-benzocyclobutenes ( 8, 9, 10 ), on heating in diluted decane solution at 175–185°, rearrange to the corresponding 3-substituted isochromenes ( 11, 12, 13 ).     

Thermisches Verhalten und Kristallstruktur von YAl3Cl12

Thermal Behaviour and Crystal Structure of YAl₃Cl₁₂ We determined the thermodynamic data of YAl₃Cl₁₂ ΔH = ?739.9 ± 3 kcal/mol and S = 136.1 ± 4 cal/K · mol by total pressure measurements and ΔH = ?739.1 ± 1.6 kcal/mol by solution calorimetry. Using DTA-investigations we established the phase diagram in the system AlCl₃–YCl₃. The crystal structure was refined on the basis of single crystal data (P3₁ 12; Z = 3; a = 1 046.8(2); c = 1 562.3(3) pm).     

Thermisches Verhalten und Thermochromie von Übergangsmetallkomplexen pyridylsubstituierter Sulfonamide

Thermal Behavior and Thermochromism of Transition Metal Complexes of Pyridyl Substituted Sulfonamides The thermal behavior of 1,2-complexes of nickel(II), copper(II) and cobalt(II) with pyridyl substituted sulfonamides (N1NHSO₂PhH, N2NHSO₂PhH, N3NHSO₂PhH and N1SO₂NHPhH) is studied between 20° and 600°C by TG, DTG, and DTA and more precisely characterized by identification of volatile decomposition products. In general the thermal decomposition starts by the reaction of one of the ligands with coordinated water or with the water vapor of air. Undecomposed N1NHSO₂PhH and N3NHSO₂PhH pass over to the vapor-phase, in the other cases the elimination is connected with a hydrolytic cleavage of the ligand. The thermal decomposition of Ni(N1NSO₂PhH)₂(NH₃)₂ is initiated by a transamidation. A study of Ni(N1NSO₂PhH)₂ demonstrates the influence of reaction conditions on the course of thermal decomposition. As far as milligram amounts are used, hydrolysis by the water vapor of air is dominating; but sulfur dioxide is eliminated when working in a preperative scale. The thermochromism of Ni(N2NSO₂PhMe)₂(H₂O)₂ goes back to the reversible transition of coordination water to lattice water. This is the first example of isomerism of the Lifschitz-type in the field of neutral chelates.     

Zur Kenntnis des Sedimentationsverhaltens von Pigmenten

Zusammenfassung Zur Charakterisierung von Grenzflächenwechselwirkungen zwischen organischen Flüssigkeiten und anorganischen Pigmenten (Ultramarinblau) wird das Sedimentationsverhalten untersucht.Es wird gezeigt, daß sich die experimentellen Ergebnisse als Folge der Tendenz der Flüssigkeiten deuten lassen, über Wasserstoffbrücken zum einen innerhalb der Flüssigkeit zu assoziieren und zum anderen die Pigmentoberfläche zu benetzen.Es kann so erklärt werden, weshalb das Sedimentationsverhalten sich fast ausschließlich durch die Variation des Löslichkeitsparameters _H bestimmen läßt.Minimale Flockungsneigung liegt nach diesen Überlegungen dann vor, wenn gute Benetzungsfähigkeit über Wasserstoffbrücken neben geringer Eigenassoziation der Flüssigkeiten vorliegt.

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Summary For analysing interface interactions of organic liquids and inorganic pigments (ultramarine blue) the sedimentation behaviour was examined. It could be demonstrated that the experimental results can be interpreted as a consequence of the tendency of the liquids to associate by hydrogen bonds within the liquid and of wetting the pigment's surface, respectively.Therefore it can be explained why the sedimentation behaviour almost exclusively can be determined by variation of the solubility parameter 6K.These considerations suggest that minimum flocculation tendency is achieved when good wettability by hydrogen bonds and low self-association of the liquid is present.

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Mit 7 Abbildungen und 3 Tabellen     

Die Verarbeitung von Pigmenten zu Anstrichstoffen

Ohne Zusammenfassung     

Darstellung,Thermisches Verhalten und Gitterparameter von Erbiumfluorooxalattetrahydrat ErFC2O4 · 4H2O

Zusammenfassung Erbiumfluorhydrat ErF₃ · 1.1 H₂O bildet in Oxalsäurelösungen Erbiumfluorooxalattetrahydrat ErFC₂O₄ · 4 H₂O. Das ErFC₂O₄ · 4 H₂O ist grobkristallin, unlöslich in verdünnten Säuren und Laugen und löslich in konzentrierter Schwefelsäure. Beim thermogravimetrischen Abbau bildet es die Verbindungen ErFC₂O₄ · 2 H₂O, ErFC₂O₄ · · H₂O, ErFC₂O₄, ErOF und ErO_1.5. Die Kristallstruktur des ErFC₂O₄ · 4 H₂O ist orthorhombisch mit den Gitterkonstantena=11.217±0.007 Å,b-13.046±0.008 Å,c=9.191±0.005 Å undZ=6.

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Erbium fluoride hydrate ErF₃ · 1.1 H₂O forms in solutions of oxalic acid erbium fluorooxalate tetrahydrate ErFC₂O₄ · 4 H₂O. The ErFC₂O₄ · 4 H₂O is coarse-crystalline, insoluble in diluted acids and bases and soluble in concentrated sulphuric acid. During thermal decomposition ErFC₂O₄ · 2 H₂O, ErFC₂O₄ · H₂O, ErFC₂O₄, ErOF and ErO_1.5 are formed. The crystal structure of ErFC₂O₄ · 4H₂O is orthorhombic, with lattice constantsa=11.217±0.007 Å,b=13.046±0.008, Å c=9.191±±0.005Å andZ=6.

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Résumé Le fluorure d'erbium hydraté (ErF₃ · 1.1 H₂O) forme dans l'acide oxalique fluorooxalate d'erbium tétrahydraté (ErFC₂O₄ · 4 H₂O), un précipité consistant à gros cristaux insoluble dans les acides et bases dilués, mais soluble dans l'acide sulfurique concentré. Au cours de sa décomposition thermique on obtient ErFC₂O₄ · 2 H₂O; ErFC₂O₄ · H₂O; ErFC₂O₄, ErOF et ErO_1.5. ErFC₂O₄ · 4 H₂O a une structure cristalline ortorhombique avec les paramètres suivants:a=11.217±0.007 Å,b=13.046±0.008 Å,c-9.191 ±0.005 Å,Z=6.

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ErF₃ · 1.1 H₂O, ErFC₂O₄ · 4H₂O. ErFC₂O₄ · 4H₂O, - , , . : ErFC₂O₄ · 2H₂O. ErFC₂O₄ · H₂O, ErFC₂O₄, ErOF ErO_1·5. ErFC₂O₄ · 4 H₂O a=11,217±0,007 Å,b=13,046±0,008 Å,c=9,191± 0,005 Å Z=6.

     

Thermisches Verhalten von o-Dipropenylbenzol,Beispiel einer aromatischen [1,7]-sigmatropischen H-Verschiebung. Vorläufige Mitteilung

cis, cis-, cis, trans- and trans, trans-o-Dipropenylbenzene (cis, cis-, cis, trans- and trans, trans- 1 ) were prepared. At 225° cis, cis- 1 isomerises to give cis, trans- 1 and vice versa. The isomerisation follows 1. order kinetics. At equilibrium 89% cis, trans- and 11% cis, cis- 1 are present. It is shown by deuterium labelling that the isomerisation is due to aromatic [1, 7 a] sigmatropic H-shifts. trans, trans- 1 rearranges at 225° to yield 2, 3-dimethyl-1, 2-dihydronaphthalene ( 3 ). This can be visualized by disrotatory ring closure of trans, trans- 1 followed by an aromatic [1, 5 s] H-shift. When cis, cis- or cis, trans- 1 are heated for 153 hrs at 225° a small amount (3%) of 1-ethyl-1,2-dihydronaphthalene ( 5 ) is formed.     

Die Methode zur Extraktion von Pigmenten aus pflanzlichem Material

Analytical and Bioanalytical Chemistry -     

Die Methode zur Extraktion von Pigmenten aus pflanzlichem Material

Ohne Zusammenfassung     

Thermisches Verhalten von Mesitylallenen; Beispiel einer aromatischen [1, 5s]-sigmatropischen H-Verschiebung. Vorläufige Mitteilung

Mesitylallene ( 6a ), 1-mesityl-3-methyl-allene ( 6b ) and 1-mesityl-3, 3-dimethylallene ( 6c ) were prepared via dienol-benzene-rearrangements. At 170° 6a isomerises to give 5, 7-dimethyl-1, 2-dihydronaphthalene ( 8 ). Under the same conditions 6b rearranges to give 2, 5, 7-trimethyl-1, 2-dihydronaphthalene ( 10 ; 60%) and cis-1-mesitylbuta-1, 3-diene ( 11 ; 40%) while 6c gives only cis-1-mesityl-3-methyl-buta-1, 3-diene ( 13 ). The allenes undergo first an aromatic [1, 5 s]-sigmatropic H-shift to the o-xylylene derivatives 7, 9 and 12 , which then exhibit disrotatory ring closure to the dihydronaphthalenes or aromatic [1, 7 a]-sigmatropic H-shift to the 1-mesitylbuta-1, 3-dienes.     

Polarographisches Verhalten von Dicyanmethanidooxoanionen

The polarographic behaviour of the anions nitrosodicyanmethanide and nitrodicyanmethanide is described. Contrary to the homologous oxoanions nitrite and nitrate the dicyanmethanidooxoanions are reduced, hydroxylamine being formed as an intermediate product, The results are discussed, assuming an influence of the asymmetric structure of the anions.     

Polarographisches Verhalten von Alkyl-Phthalatestern

Ohne Zusammenfassung     

Thermisches Verhalten von Caesiumchloroferraten(III) und Caesiumchloroferrat(III)-Hydraten Zum Phasendiagramm des Systems CsCl?FeCl3

Thermal Behaviour of Cesium Chloroferrates(III) and Cesium Chloroferrate(III) Hydrates. On the Phase Diagram of the CsCl? FeCl₃ System The thermal behaviour of CsFeCl₄, Cs₂Fe(H₂O)Cl₅, and Cs₃FeCl₆ · H₂O has been studied by simultaneous thermal analysis up to 500°C, x-ray diffraction, and Raman spectroscopy. Anhydrous Cs₃FeCl₆ is metastable up to 280°C. Anhydrous Cs₂FeCl₅ does not exist. The decomposition of Cs₃Fe₂Cl₉ at 270°C yields CsCl and CsFeCl₄. This solid phase reaction is reversible. The corrected phase diagram of the system CsCl? FeCl₃ is presented basing on experimental results.     

Dielektrisches Verhalten von Ichthyolsalben

Ohne ZusammenfassungHerrn Dr. Schmidt aus Oberbruch, Bez. Aachen, danke ich herzlich, daß er das Vorlesen dieses Vertrags übernommen hat.