Die Verteilungskoeffizienten von Dysprosium-, Erbium- und Yttriumnitrat zwischen Tri-n-butylphosphat und 9–12M-Salpetersäure

The distribution coefficients for the nitrates of Dy, Er and Y betweenTBP and 9, 10, 11, and 12M-HNO₃ were determined for a wide range of concentrations (20°C). The distribution coefficients of yttrium nitrate were within the experimental error equal to those of erbium nitrate. The separation factors Y/Dy and Er/Dy, resp., showed a flat maximum at 10M-HNO₃. By adding NH₄NO₃ (1M) to 10M-HNO₃ the distribution coefficients were lowered in the same proportion, as to leave the separation factors unchanged.

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Mit 5 Abbildungen

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Craig-Verteilung von Seltenerdelementen im System Tri-n-butyl-phosphat-Salpetersäure, 6. Mitt.     

Fluordiazadiphosphetidine, 18. Mitt. Neue zwitterionische Fluordiazadiphosphetidinderivate

The reaction of (CH₃NPF₃)₂ with substituted hydrazines yields a new type of a P/N/P/N ring system by addition of one molecule hydrogenfluorid to the substituted molecule. These betain-like compounds are the first examples of a P/N/P/N ring system with one P-atom in ⁵- and the other in ⁶-conformation.

     

Benzodifurans. I. The synthesis of benzo[1,2-b:5,4-b]difuran and some methyl analogs

The first parent benzodifuran (XVI) and three di- and trimethylated derivatives have been synthesized and screened for erythemal activity (negative response). Two benzodifurans were prepared from resorcinol and 2-methylresorcinol by acetylation, Fries rearrangement, alkylation of the resulting 4,6-diacetylresorcinols with ethyl bromoacetate, saponification, and then cyclization of the (4,6-diacetyl-1,3-phenylenedioxy)diacetic acids. Another was prepared from the Claisen rearrangement product of 1,3-bis(allyloxy)-2-methylbenzene by acetylation, bromina-tion, and cyclization. Ozonolysis of the Claisen rearrangement product gave additional support to the formulation of o-hydroxyphenylaeetaldehydes as cyclic hemiacetals. The parent benzodifuran was synthesized from 5-formyI-6-hydroxybenzofuran, which was prepared in two steps from 5-bromo-6-methoxybenzofuran. Alkylation of the former with ethyl bromoacetate, saponification, and cyclization furnished benzo[1,2-b.5,4-b ]difuran. The ultraviolet and nuclear magnetic resonance spectra of the four benzodifurans are compared.     

Isolation of a stable 1-iridabicyclo[3.2.0]hepta-1,3,6-triene and its reversible transformation into an iridacycloheptatriene

Reaction of the iridacyclopentadiene complex 2 with 2-butyne yields a mixture in equilibrium of the iridacycloheptatriene 3 and a novel 1-iridabicyclo[3.2.0]hepta-1,3,6-triene, 4.     

Thioreductones and Derivatives (G)

Thioreductones and Derivatives . Replacement of one or two (principally also three) O‐atoms in aci‐reductones by sulfur leads to the corresponding thioreductones. In the present paper, different methods of their synthesis are discussed. Substitution of the bromo nucleofug in the 2‐position of 1,3‐dicarbonyl compounds as well as of a 3‐oxosulfone by selected sulfur nucleophiles is assumed to follow an S_RN1 pathway. Characteristic properties, some typical reactions, and selected derivatives were studied. S‐Alkyl‐ and S‐aryl‐substituted cyclic 2‐thioreductones have been found to be synthons for the preparation of vinylogous reductones (2,3‐diacyl‐1,4‐dihydroxy‐1,3‐dienes) and of tetraacyl ethylenes as their bis‐dehydro products.     

[{Cp(CO)3Mo}4In4(PSiMe3)4], Ein metallorganisch substituiertes In4P4-Heterokuban

[{Cp(CO)₃Mo}₄In₄(PSiMe₃)₄], an Organometallic In₄P₄-Heterocubane [{Cp(CO)₃Mo}InCl₂] reacts with P(SiMe₃)₃ in THF as solvent to form [{Cp(CO)₃Mo}₄In₄(PSiMe₃)₄] 1. 1 crystallizes in the space group P1 . The lattice constants (at 208 K) are: a = 1 770.1(6), b = 1 490.3(6), c = 1 317.5(6) pm, α = 76.59(4),β = 88.54(3), γ = 88.98(3)°. According to the crystal structure analysis, 1 contains a slightly distorted In₄P₄-core with an alternating arrangement of In and P atoms. The In atoms are coordinated roughly tetrahedrally by three PSiMe₃ groups (In–P: 256.9(3)–262.3(3) pm) and a {Cp(CO)₃Mo} substituent (In? Mo: 278.0(2)–279.5(3) pm).     

PPh3Me[MoBr5(CH3CN)]. IR-Spektrum,magnetisches Verhalten und Kristallstruktur

PPh₃Me[MoBr₅(CH₃CN)]. I.R. Spectrum, Magnetic Behaviour, and Crystal Structure Molybdenum tetrabromide and acetonitrile form MoBr₄(CH₃CN)₂, from which PPh₃Me[MoBr₅(CH₃CN)] is obtained by reaction with PPh₃MeBr in dibromo methane. Both compounds are characterized by their IR spectra. By evaluation of the magnetic susceptibility of PPh₃Me[MoBr₅(CH₃CN)] in the temperature range of 4.2 to 290 K the Curie-Weiss parameters μ_cw = 2.65 B.M. and Θ = ?44 K were obtained. The crystal structure of PPh₃Me[MoBr₅(CH₃CN)] was determined by X-ray diffraction (2426 observed reflexions, R = 0.082). Crystal data: a = 1064.9, b = 2172.1, c = 1330.4 pm, β = 119.92º, space group P2₁/c, Z = 4. In the crystal, PPh₃Me⁺ and [MoBr₅(CH₃CN)]^? ions are packed in alternate cation and anion layers perpendicular to a. In the anion the Mo atom has a distorted octahedral coordination. The bond length of the bromine atom in trans position to the N atom is considerably shorter than the other MoBr distances.     

Fluordiazadiphosphetidine, 5. Mitt.

Reaction of (CH₃NPF₃)₂ with equimolar amounts of N-methylhexamethyldisilazane yields a reaction product, which can be separated in a polymer and a crystalline fraction. High-vacuum sublimation of the crystalline part yields the already known compound (CH₃N)₄P₃F₇, the new spiro-isomer F₃P(CH₃N)₂PF(CH₃N)₂PF₃ and the spiro-compound F₃P(CH₃N)₂PF(CH₃N)₂PF(CH₃N)₂PF₃, an isomer of the known compound (CH₃N)₆P₄F₈.     

Kinematographische Quellungsanalyse im Dunkelfeld unter Verwendung des Mikromanipulators. I

Ohne Zusammenfassung über diese Untersuchung wurde bei gleich-, zeitiger Vorführung des Kinofilmes am 18. 3. 1933 von K. He? vor der kolloidchemischen Sektion der holl?ndischen chemischen Gesellschaft, am 15. 5. 1933 im Colloquium des Kaiser-Wilhelm-Institut für physikalische Chemie und Elektrochemie, sowie am 10. 7. 1933 in der Juli-Sitzung der Deutschen chemischen Gesellschaft berichtet. Für die überlassung optischer Instrumente zur Durchführung der Untersuchungen im Dunkelfeld sind wir der Deutschen Gemeinschaft zur Erhaltung und F?rderung der Forschung zu aufrichtigem Dank verpflichtet. Der I. G. Farbenindustrie A. G. und im besonderen Herrn Direktor Dr. Gajewski danken wir für die überlassung von Filmmaterial für die Kinoaufnahme.     

Veränderungen der Baumwollzellulose durch Färbevorgänge

Ohne Zusammenfassung 8. Mitteilung von K. Brass, Untersuchungen über das Zustandekommen von F?rbungen [7. Mitteilung siehe K. Brass und R. Smrček, Ber. Dtsch. chem. Ges.75, 1680 (1942)].