Über cyclische tertiäre Arsine und sekundäre Arsenoxide

α,ω-Alkane-bis-diphenylarsines and -dimethylarsines, R₂AsC_nH_2nAsR₂, may be obtained from dichloroalkanes and sodium diorganyl-arsenides, R₂AsNa. The latter are prepared from tetraphenyl- and tetramethyl-diarsenic-sulphide, respectively, (R₂As)₂S. Elemental sodium eliminates on each As atom of the tetraphenyl-diarseno-alkanes one phenyl group, and on oxidation α,ω-alkane-diphenylarsenic acids are obtained. Reduction of these acids by means of SO₂ yields cyclic, secondary arsenic oxides, whereas H₃PO₂ gives cyclic arsines with As ? As bonds. Disodium-phenylarsenide, C₆H₅AsNa₂, prepared from (C₆H₅AsS)₄, reacts with longer dichloroalkanes to form cyclic tertiary phenylarsines which may contain, in addition to As, further heteroatoms such as N, O or S. Those arsines, which only contain carbon as the ring atoms, commutate with AsCl₃ to 1-chloro-arsolane and 1-chloroarsenane.     

Über primäre Disazofarbstoffe mit Aminonaphtol-sulfonsäuren

Disazo dyes from 6-amino-1-hydroxy-naphthalene-3-sulfonic acid (J acid) were synthesized by coupling ortho-hydroxy monoazo dyes with different diazonium compounds in acid medium (dyes No 3 – 14 . A second coupling to the ortho position of the amino group was also possible with the copper complexes of o,o' -dihydroxy monoazo dyes from 8-amino-1-hydroxynaphthalene-3,6-disulfonic acid (H acid) dyes No 19 – 22 ). This is a reversal of the well known rule that the formation of disazo dyes with aminonaphthol-sulfonic acids is only practicable when an acid coupling is followed by an alkaline one. 5-Amino-1-hydroxy-naphthalene-3-sulfonic acid (M acid), which is said to form no disazo dyes, could be coupled twice with several diazonium compounds to yield disazo dyes (dyes No 24 , 26 , 27 , 29 ).     

Ternäre Thallium-Indium-Sulfide: Eine Zusammenfassung

Ternary Thallium Indium Sulfides: A Summary Combined thermal and X-Ray analyses in the ternary system Thallium—Indium—Sulfur show, that the two binary sections Tl₂S? In₂S₃ and TlS? InS contain ternary compounds with unique crystal structures. The chemical formulas of these ternary solids are TlIn₅S₈, TlIn₃S₅, TlInS₂ and Tl₃InS₃ for the section Tl₂S? In₂S₃ and TlIn₅S₆ as well as Tl₃In₅S₈ (metastable high temperature phase) for the section TlS? InS respectively. With TlIn₅S₇ an additional ternary solid could be detected, which is located outside the two sections. It is derived from the binary mixed valence compound In₆S₇ by complete substitution of In⁺ by Tl⁺. The following ionic formulations make the mixed valence character of the ternary Thallium—Indium-Sulfides reasonable: TlIn₅S₈ = Tl⁺(In³⁺)₅(S^2?)₈, TlIn₃S₅ = Tl⁺ (In³⁺)₃(S^2?)₅, TlInS₂ = Tl⁺In³⁺(S^2?)₂, Tl₃InS₃ = (Tl⁺)₃In³⁺ · (S^2?)₃, TlIn₅S₆ = Tl⁺([In₂]⁴⁺)₂In³⁺ (S^2?)₆, Tl₃In₅S₈ = 4 × [(Tl⁺)_0,75 · (In⁺)_0,25In³⁺(S^2?)₂], TlIn₅S₇ = Tl⁺[In₂]⁴⁺ (In³⁺)₃(S^2?)₇. All compounds contain Tl⁺-ions in a characteristic “lone pair coordination” of S^2? ions. Indium atoms however occur with the oxidation numbers +2 (formal, In₂ dumb bells with covalent In? In bonding) and +3 (with In³⁺ in tetrahedral and octahedral coordination of S^2?). Chemical preparation, crystal chemistry and general properties of the ternary solids are discussed, summarized and compared to each other.     

Ternäre Phasen im Dreistoffsystem Lithium-Gallium-Germanium

Ternary Phases in the System Lithium—Gallium—Germanium The crystal structure of the ternary compound LiGaGe was refined by Fourier synthesis. The space-group of the structure is Nr. 186 (P6₃mc–C), and the Ga and Ge atoms form a Wurtzite lattice, the octahedral sites of which are occupied by the Li atoms. The homogeneity range of the compound LiGaGe was investigated, several further ternary phases with a cubic-fc. lattice could be found in the Li? Ga? Ge system.