Darstellung und Eigenschaften von Trimethyl-(dialkylamidosulfonyl)-ammoniumhalogeniden

Zusammenfassung Aus Dialkylamidosulfochloriden oder-bromiden und Trimethylamin werden thermisch stabile kristalline 11-Additions-verbindungen (Tab. 1) erhalten, die auf Grund von IR-Spektren due Sulfonylammonium-Struktur [R₂NSO₂N(CH₃)₃]⁺ X ^– besitzen. Verglichen mit den zugrunde liegenden Sulfohalogeniden sind sie durch eine erhöhte Reaktionsfähigkeit der Halogenatome gekennzeichnet. Beschrieben werden die Thermolyse und die Reaktionen dieser Verbindungen mit einigen protonenaktiven Stoffen (Wasser, Äthanol, Phenol, Thiophenol). Mit Hexamethyldisilazan liefern sie N,N-Dialkyl-N-trimethylsilylsulfamide, während die freien Sulfohalogenide auch bei erhöhter Temperatur nicht mit dem Disilazan reagieren.

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Synthesis and properties of trimethyl-(dialkylamidosulphonyl)-ammonium halides

Treatment of dialkylamidosulphonyl chlorides or bromides with trimethylamine affords stable crystalline 11 addition compounds of the general formula [R₂NSO₂N(CH₃)₃]⁺ X ^– (cf. Table 1). Evidence for this formulation is obtained from IR spectra. A striking difference between these compounds and the parent sulphonyl halides is the enhanced reactivity of the halogen groups. The thermal degradation and the reactions of the complexes with water, ethanol, phenol, thiophenol, and hexamethyldisilazane are reported. The latter reaction yields N.N-dialkyl-N-trimethylsilyl sulphamides, whereas the corresponding free dialkylamidosulphonyl chlorides are recovered unchanged from refluxing hexamethyldisilazane.

     

Synthese von Betenamin und von Betalain-Modellsubstanzen

Synthesis of Betenamine and of Betalaine Model Substances For comparisons of color, spectroscopic properties, pK_a values, and stabilities, a number of model substances containing the 1,7-diazaheptamethinium chromophore 8 of the yellow and red betalaine plant pigments were prepared by the thermal or photolytic ring opening of simple pyridine derivatives (such as 2 and 14-16 ), followed by the introduction of amines. Among the novel compounds prepared were betenamine perchlorate ( 5 ), the ‘naked’ ring system of the beet-pigment betanine ( C ) as well as two 1,7-diazaheptamethinium salts 25 and 27 with terminal amono acids. The synthesis of 5 started with 4-(2-aminoethyl)pyridine ( 1 ) and proceeded via 2 , ring opening with indoline to 4 , saponification, and intramolecular amine replacement (Scheme 1). The syntheses of 25 and 27 involved only one step, namely ring opening of γ-picoline using (S)-cyclodopa ( 24 ) and (S)-proline ( 26 ), respectively (Scheme 3).     

Synthese und Charakterisierung von Quecksilbercyanamid

Synthesis and Characterisation of Mercury Cyanamide HgCN₂ was prepared by double conversion of HgCl₂ with sodium cyanamide in aqueous solution. Its crystal structure has been determined using X‐ray powder data and refined by combined profile fits using X‐ray and neutron diffraction data (Pbca, Z = 8, a = 10.4851(1), b = 6.5138(1), c = 6.8929(1) Å; R_p (X‐ray) = 6.15%; R_p (neutrons) = 2.33; 2.43%). The cyanamide‐anion is bent (172.4(7)°), which has been confirmed by vibrational spectroscopy. Mercury and carbon form zigzag chains. Not including nitrogen, the structure is related to the MnP‐structure type.     

Synthese von Organometall- und Metall-Phenylcarbodiimiden

Synthesis and structure of some organometallic phenylcarbodiimides R₃SiNCNC₆H₅, R₂Si(NCNC₆H₅)₂, of As(NCNC₆H₅)₃, Sb(NCNC₆H₅)₃ and of some d-metal phenylcarbodiimides, M(NCNC₆H₅)_n (n = 1.2), are reported.     

Synthese und Kristallstruktur von Tetramethylammonium-Gismondin

A new synthetic zeolite, (CH₃)₄NA1Si₃O₈, H₂O, has been synthesized and shown to be an isotype of the mineral gismondine, CaAl₂Si₂O₈,4H₂O. Sodium and other cations can be introduced by ion exchange after thermal decomposition of the organic cation. A continuous structural change to «cubic» NaP has thereby been recorded, which indicates that the latter is also based on a gismondine-type aluminosilicate framework. The crystal structure of tetramethylammonium-gismondine has been determined using X-ray powder data supplemented by electron diffraction. The crystals are tetragonal, a = 9.84 and c = 10.02 Å, with 4 formula units per unit cell. The apparent symmetry of the framework structure is I4₁/amd, however, this is violated by the organic cation. Two of the methyl groups are pointing to oxygen atoms of the framework and the short methyl-oxygen distances indicate C? H ? O interaction.     

Synthese und Kristallstruktur von N-Formylformamidinium-hexachloroantimonat

Synthesis and X-Ray Structure Determination of N-Formylformamidinium Hexachloroantimonate The title compound is formed in high yields by the interaction of [Cl₂CH? NH? CH?NH₂][SbCl₆] with SO₂ in CH₂Cl₂ solution. According to the spectra (i.r. and ¹H-n.m.r.) the cation [O?CH? NH? CH?NH₂]⁺ exists in an almost planar, all-cisoide conformation. The hexachloroantimonate crystallizes in the orthorhombic space group Pna2₁ with 4 formula units per cell. The anion-cation cross-linkage by relative short NH…?Cl(Sb) bridges is remarkable. The structure was refined to an R value of 0.027.