Kristallstrukturen von [TiF3(NPPh3)(HNPPh3)]2 und von HNPPh3

Crystal Structures of [TiF₃(NPPh₃)(HNPPh₃)]₂ and of HNPPh₃ The phosphoraneiminato-phosphaneimine complex [TiF₃(NPPh₃)(HNPPh₃)]₂ was obtained by the reaction of TiF₄ with Me₃SiNPPh₃ in boiling dichloromethane. It crystallizes from 1,2-dichloroethane as yellow crystals which include four molecules C₂H₄Cl₂ per dimeric formula unit. Space group P2₁/n, Z = 2, structure solution with 7270 independent reflections, R = 0.060 for reflections with I > 2σ(I). Lattice dimensions at ?50°C: a = 1417.5, b = 1896.9, c = 1586.6 pm, β = 101.22°. The compound forms centrosymmetric dimeric molecules via μ₂-F bridges with TiF distances of 194.6 and 223.3 pm, the longer one being in trans-position to the N atom of the (NPPh₃)^? ligand. Its TiN bond length of 177.7 pm corresponds with a double bond. The TiN bond length of the HNPPh₃ donor molecule of 213.4 pm is typical for a donor acceptor bond. According to the crystal structure determination the phosphaneimine HNPPh₃ forms monomeric molecules without intermolecular hydrogen bridges with a PN bond length of 152.4 pm. Space group P2₁/c, Z = 4, structure solution with 3229 independent reflections, R = 0.062 for reflections with I > 2σ(I). Lattice dimensions at ?70°C: a = 1460.4, b = 928.9, c = 1096.6 pm, β = 93.35°.     

Synthese von 3-Oxacholestanen

Successive treatment of 5α-cholestan-3-one ( 1 ) with O₂ under basic conditions and then NaBH₄ led to 5α-3-oxa-cholestan-2-one ( 5 ). Analogous reactions with 5β-cholestan-3-one ( 6 ) yielded 5α-4-oxa-cholestan-3-one ( 7 ) and 5 ξ-3-oxa-cholestan-4-one ( 8 ). 4-Cholesten-2-one ( 10 ), which was prepared starting from 4-cholesten-3-one, was isomerized by methanolic KOH to give a mixture of 5α-cholest-3-en-2-one ( 11 ) and 5β-cholest-3-en-2-one ( 12 ). 5β-Cholestane-2,3-dione ( 17 ) was synthesized from 4β-bromo-5β-cholestan-3-one ( 13 ). Ozonolysis of the dione 17 and subsequent NaBH₄ reduction of the oxidation product gave both 5β-2-oxa-cholestan-3-one ( 18 ) and 5β-3-oxa-cholestan-2-one ( 19 ).     

Die Kristallstruktur von TlFe3Te3

TlFe₃Te₃ is hexagonal, space groupP6₃/m–C _2h ⁶ ,a=9.350(2) Å,c=4.2230 (7) Å,Z=2. Iron and tellurium atoms occupy the positions 6 (h) withx=0.170,y=0.149 andx=0.046,y=0.357 respectively. Thallium atoms are situated in 2 (d). The structure was determined on the basis of single crystal data obtained form a four circle diffractometer. Refinement yielded andR-value of 4.8% for an asymmetric set of 267 reflections. TlFe₃Te₃ is a new structure type. The structure and its relations to the Mn₅Si_3–, the Nb₃Te₄-and the Tl _x V₆S₈-type are discussed.

     

Neue Derivate von 3, 3-Dimethylindolinonen

Ohne Zusammenfassung     

Neue Derivate von 3, 3-Dimethylindolinonen

Ohne ZusammenfassungI. Mitteilung: Monatsh. Chem.58, 1931, S. 369, bzw. Sitzb. Ak. Wiss. Wien (IIb)140, 1931, S. 369. In der ersten Mitteilung wurde auf S. 370 erwähnt, daß in der zweiten Mitteilung im kurzen Auszuge ein Kapitel über Thioindolinone folgen werde, welches schon im Jahre 1914 von meinem Sohne Walter abgeschlossen wurde.     

Eine einfache synthese von 3-borolenen. Die darstellung von 1-phenyl-3-borolen

The reactions of (1,3-diene)magnesium addition compounds with boron halides provide a simple route to 3-borolenes. 1-Phenyl-3-borolene, its trimethylamine adduct and tetramethylammonium (1,1-diphenylborata-3cyclopentene) are described in detail.     

Die Bestimmung von 3-Chlorpropen

Ohne Zusammenfassung     

Zur Kristallstruktur von CuGeO3

The crystal structure of CuGeO₃ (D _2h ⁵ -Pbmm) has been redetermined by means of 3-dimensional Fourier syntheses. The structure is built up by [CuO₄]- and [GeO₃]-chains (Einereinfachkette). The interatomic distances are found to be: Ge?O: 1,76₉ (2x) and 1,72₄ (2x) Å; Cu?O: 1,94₂ (4x) and 2,76₆ (2x) Å.     

Metallkomplexe von N-substituierten 3-Imino-isoindolinonen

Metal Complexes of N-substituted 3-Imino-isoindolinones The condensation of 3-imino-isoindolinone 4 and benzimidazoles or benzthiazoles containing activated methyl-, methylen- or aminogroups ( 5 resp. 6 ), yields the iso-indolinone-ligands 1 and 2. Metal ions such as Co²⁺, Ni²⁺, Cu²⁺ and Zn²⁺ form (1:2)-complexes with these ligands of very high chemical and photochemical stabilities. The magnetic properties of these complexes indicate that the geometry around the central atoms is distorted tetrahedral. A X-ray diffraction study of one of the Co(II)-complexes confirms these findings.     

Photoreaktionen von 3-substituierten Cumarinen

Photoreactions of 3-substituted Coumarins UV.-irradiation of 3-acetylcoumarin in 2-propanol gives the dihydrodimer 2 . In benzene solutions 2- and 4-vinylpyridine, 1,1-dichloro-ethylene, 2,3-dimethylbutadiene, vinylene carbonate and cyclohexene add to 3-acetylcoumarin and 3-methoxycarbonylcoumarin yielding the cyclobutanes 4 to 11 .     

Der Triplettzustand von 3-Nitropyren

Ohne Zusammenfassung     

Eine neue Synthese von 3-Aminoisoxazolen1 und 3-Aminoisoxazolinen mit Hilfe von N-Hydroxyharnstoff

Zusammenfassung Die Reaktion von N-Hydroxyharnstoff mit Crotonsäurenitril oder Allylcyanid führte zum 3-Amino-5-methyl-4,5-dihydroisoxazol, welches sich nicht zum 3-Amino-5-methylisoxazol dehydrieren ließ. Letztere Verbindung ist jedoch durch entsprechende Umsetzung von 2,3-Dibrombuttersäurenitril zugänglich. Diese Synthese wurde auf weitere ,-Dibromcarbonsäurenitrile ausgedehnt. Als Ringschlußkomponente war N-Hydroxyharnstoff dem Hydroxylamin stets weit überlegen. Als cyclischer Vertreter der Dibromcarbonsäurenitrile ergab das 1-Cyan-1,2-dibromcyclohexan — in alkalischer Lösung mit Hydroxyharnstoff umgesetzt — in anormaler Reaktion — das 3-Amino-5,6,7,7a-tetrahydro-1,2-benzisoxazol (13), anstelle des erwarteten 3-Aminotetramethylenisoxazols (14). Für das isomere 5-Aminotetramethylenisoxazol (15) wird eine verbesserte Synthese gegeben.

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A novel synthesis of 3-aminoisoxazoles¹ and 3-aminoisoxazolines starting with N-hydroxyurea

3-Amino-5-methyl-4,5-dihydroisoxazole (1) was obtained from N-hydroxyurea and crotononitrile or allyl cyanide in alkaline solution. Use of hydroxylamine, however, gave only low yields of1. Attempts on an preparative scale to dehydrogenate1 to 3-amino-5-methylisoxazole (2) failed with the free compound as well as with its benzenesulfonamide derivatives.The 3-aminoisoxazoles2, 7, 9 and12 were found to be accessible without dehydrogenation by direct cyclization of 2.3-dibromocarbonitriles with N-hydroxyurea. Again, use of hydroxylamine instead of N-hydroxyurea gave only low yields or led to mixtures of 3-amino- and 5-aminoisoxazoles.The cyclic dibromocarbonitrile 1-cyano-1.2-dibromocyclohexane reacted anomalously to give 3-amino-5,6,7,7a-tetrahydro-1,2-benzisoxazole (13) instead of the expected 3-aminotetramethyleneisoxazole (14). An improved synthesis of the isomeric 5-aminotetramethyleneisoxazole (15) is described.

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Herrn Dr.O. Isler zum 60. Geburtstag in Verehrung gewidmet.     

Struktur und Eigenschaften von Doppelhalogeniden von substituiertem Ammonium und Quecksilber(II). V. Die Kristallstruktur von CH3NH3HgBr3 und CH3NH3HgI3

Structure and Properties of Double Halogenides of Substituted Ammonium and Mercury(II). V. Crystal Structure of CH₃NH₃HgBr₃ and CH₃NH₃HgI₃ The compounds CH₃NH₃HgBr₃ and CH₃NH₃HgI₃ were prepared from stoichiometric mixtures of the methylammonium halogenides and the mercury(II) halogenides in methanol by evaporation. X-ray structure determination revealed orthorhombic symmetry with space group Cmcm for CH₃NH₃HgBr₃. The environment of mercury is trigonal bipyramidal with Hg? Br distances from 2.527(2) to 2.565(2) Å (equatorial) and 3.192(2) Å (axial). The bipyramids form double chains //c with the CH₃NH₃^⊕ cations between them. The structure of CH₃NH₃HgI₃ is monoclinic, space group P2₁/n with chains of corner sharing distorted tetrahedra //b. The Hg–I distances in the tetrahedron are between 2.708(3) Å and 2.777(3) Å.     

Die Kristallstruktur von BaTeO3

Crystal Structure of BaTeO₃ Crystals of BaTeO₃ were prepared from melts. BaTeO₃ is isotropic with KClO₃ and crystallizes in the monoclinic system, space group P2₁/m. The lattice parameters are a = 4.63₃, b = 5.95₂, c = 7.30₈ Å, β = 111.2°. The formula unit is 2. The crystal structure was determined by Patterson synthesis, refined by least squares and confirmed by (F_o — F_c) synthesis. Using isotropic temperature corrections the R-value of 1072 observed reflections calculated as 0.748, and anisotropic the R-value as 0.702. In BaTeO₃ tellurium forms with three oxygen atoms pyramidal TeO₃-groups, barium has to oxygen atoms the coordination 7+2. The TeO₃ groups are not linked one with another, but with the BaO₉ polyhedrons by common corners and edges, the latter are linked one with another only by common edges.     

Partialsynthese von 6-epi-gibberellin-A3

$\text{2}$ is silylated, enolised with KH and converted by the addition of acid to a mixture of epimeric aldehydes $\text{2}$ and $\text{3}$. Subsequent acetylation, oxydation and deacetylation of $\text{3}$ affords 6-Epi-gibberellin-A₃ ($\text{6}$).     

Der Triplettzustand von 3-Nitropyren

Ohne Zusammenfassung     

Resonanzramanspektrum von matrixisoliertem Se3

Resonance Raman Spectrum of Matrixisolated Se₃ By the application of a double furnace it is possible to get a gas mixture of 90% Se₂ molecules and 10% Se atoms. By condensing this mixture in an inertgas matrix at 15 K followed by annealing to nearly 25 K we got Se₃ molecules by a matrix reaction In the resonance Raman spectrum of this molecule we observed 14 overtones of the symmetric stretching vibration. So we can calculate the following values of ω₁ an x₁₁ for ⁸⁰Se₃: 312.15 ± 0.2 cm^?1 and 0.53 ± 0.02 cm^?1. Using a mixture of 62% ⁷⁶Se and 38% ⁸²Se we got band structures in which the intensity of the bands and their frequency shift can only be explained by a bent Se₃ molecule (～115°). The value of the force constant f_r + f_rr is 310 ± 20 Nm^?1. — By a new construction it is possible to get the Raman and IR reflection spectrum of the same matrix.     

Die Raman-Spektren von ZnTiO3 und CdTiO3

Raman Spectra of ZnTiO₃ and CdTiO₃ The laser Raman spectra of ZnTiO₃ and CdTiO₃ are recorded and discussed with the aid of a factor group analysis and in comparison with formerly reported IR data. The results allow a better insight into the vibrational behaviour of double oxides with ilmenite structure.