Über Bleisilberphosphate mit Apatitstruktur

On Lead Silver Phosphates with the Apatite Structure The hitherto unknown leas silver phosphate (Pb₈Ag₂PO₄)₆ has been prepared. It has an apatite structure with unoccupied halide positions like the analogous lead alkali compounds and forms solid solutions with Pb₁₀(PO₄)₆O, Pb₁₀(PO₄)₆(OH)₂, and Pb₁₀(PO₄)₆Cl₂. At 800°C, Pb₈Ag₂(PO₄)₆ decomposes to solid Pb₃(PO₄)₂ and PbAgPO₄. (Pb, Ag) apatites have been precipitated from aqueous solutions. On the side being richer in Ag they can approximately be formulated as solid solutions between Pb₈Ag₂(PO₄)₆ and Pb₁₀(PO₄)₆(OH)₂. However, the i.r. spectrum reveals clear differences compared with thermal and hydrothermal preparations. The distribution of cations shows nonideal behaviour with reduced tendency for fixation of Ag⁺, if the content of Ag in the precipitate is high. The compound PbAgPO₄ decomposes below 520°C to Pb₈Ag₂(PO₄)₆ and Ag₃PO₄. The arsenate apatite Pb₈Ag₂(AsO₄)₆ decomposes below 530°C to Pb₃(AsO₄)₂ and Ag₃AsO₄.     

Über atropisomere Biphenyl-Derivate mit einer Pseudoasymmetrieachse

Diastereomeric biphenyl derivatives VIIIa and b have been prepared as first examples of compounds with an axis of pseudoasymmetry. Compound VIIIa was prepared by an unambiguous synthesis from (+)-V. The absolute configuration of the latter was determined by correlation with (+)-(R)-2-amino-2′,6-dimethyl-6′-nitro-biphenyl (XII) and hence the configuration of VIIIa (and therefore also of VIII b) was established.     

Über ternäre Thalliumchalkogenide mit Thalliumselenidstruktur

On Ternary Thallium Chalcogenides with Thallium Selenide Structure. By means of single crystal investigations, it has been confirmed that the compounds TlGaTe₂, TIInSe₂, and TIInTe₂ crystallize in the TISe type (B37). As an univalent cation thallium is surrounded by eight chalcogen atoms. Gallium and indium are trivalent with tetrahedral coordination and covalent bonds. The interatomic distances as well as coordination and bonding resulting from them are discussed.     

Über die Oxydation des O-Methylbulbocapnins mit Jod

The oxidation product obtained by treatment of bulbocapnine methyl ether ( 2a ) with iodine in ethanol/water is not the tetradehydroaporphinium salt 4 as assigned by Gadamer & Kuntze, but a dimer of structure 3 . Reduction of 3 with zinc in dilute sulfuric acid gives rac-bulbocapnine methyl ether, whereas reduction with complex hydrides affords the diastereomeric dimers 7a and 7b .     

Über die Reaktion von Thiophosphoryltrichlorid mit Hexamethyldisilazan

On the Reaction of Thiophosphoryl Chloride with Hexamethyl Disilazane On the basis of a ³¹P n.m.r. spectroscopic study of the reaction of PSCl₃ with hexamethyl disilazane a method for the preparation of Me₃SiNHP(S)Cl₂( 1 ) and the diazadiphosphetidine 2 , [Me₃SiNHP(S)?NSiMe₃]₂ has been developed. These new crystalline compounds have been characterized by i.r., Raman, ³¹P n.m.r. and mass spectroscopy, and their thermal behaviour has been studied. The formation and constitution of 2 are discussed, and its ¹H and ²⁹Si n.m.r. spectra are reported.     

Über die Reaktion von Alkalihexafluorosilicaten mit Aluminiumoxid

On Reactions of Alkali Hexafluorosilicates with Aluminum Oxides The reaction of Na- and K-hexafluorosilicates and α- or γ-Al₂O₃ has been investigated. Final reaction products are fluoroaluminates and alumosilicates. The reaction mechanism has been discussed. Influence of reaction parameters like time, temperature, layer thickness, and the effect of admixtures (fluorides, SiO₂) have been regarded. Tablet-reactions show the introduction of reaction by Si? F species.     

Über Umsetzungen von weißem Phosphor mit Metallorganylen

Reactions of White Phosphorus with Lithium Alkyls The reaction of white phosphorus with Lime (me = CH₃) (molar ratio P₄: Lime = 1:1) in DME or THF via insoluble lithium polyphosphides yields Li₃P₇ 1 , Li₂P₇me 2 and LiP₇me₂ 3 , which react with me₃SiCl or meBr to form P₇(Sime₃)₃, P₇(Sime₃)₂me and P₇me₃, respectively. All of these compounds were characterized by ³¹P-n.m.r. By higher amounts of Lime (molar ratio P₄:Lime = 1:2) Li₂P₇me is decomposed. The analogous reaction of P₄ with LiCme₃ yields Li₃P₇, LiP₇(Cme₃)₂, Li₂P₇Cme₃, and additionally LiP₄(Cme₃)₃ and LiP₃(Cme₃)₂. Again insoluble lithium polyphosphides were observed as intermediates. Addition of me₃SiCl to the reaction mixture affords P₇(Sime₃)₃, P₇(Sime₃)₂(Cme₃), P₇(Sime₃)(Cme₃)₂ P₄(Sime₃)(Cme₃)₃, and P₃(Sime₃)(Cme₃)₂. In n-hexane/THF the reaction of P₄ with LiCme₃ in the molar ratio of 1:2 predominantly yields the fourmembered ring LiP₄(Cme₃)₃ besides some of the three-membered ring LiP₃(Cme₃)₂, which with me₃SiCl yield P₄(Sime₃)(Cme₃)₃ and P₃(Sime₃)(Cme₃)₂. In addition to the mentioned main products are found: all compounds of the group P₈(Sime₃)₅(Cme₃) to P₈(Sime₃)(Cme₃)₅, the five-membered rings P₅(Sime₃)₂(Cme₃)₃ and P₅(Sime₃)₃(Cme₃)₂ as well as P(Sime₃)₂Cme₃ and P(Sime₃)₃.     

Über Phosphorstickstoff-Verbindungen XXVIII. Über Reaktionen von Cyanamid,Dicyanimid und Dicyandiamid mit PCl5

Interaction between cyanamide and PCl₅ in the mole ratio 1:3 yields the phosphazenium salt [Cl₃P?N? C(Cl)?N? PCl₃] [PCl₆]. The reaction of sodium dicyanimide and PCl₅ gives 1. 1. 3. 5-tetrachloro-1-phospha-2. 4. 6-triazine (compound B in ?Inhaltsübersicht”?). Dicyandiamide and PCl₅ (1:2) give compound C and, at milder conditions the salt-like phosphatriazine D. Solvolysis of C with formic acid or of D with sulphur dioxide yields E.     

Über die Reaktion von Phenolen mit N-substitutierten Maleinimiden

The Reaction of Phenols with N-substituted Maleinimides Phenoxysuccinimides are formed by the base catalysed addition of phenols to N-substituted maleinimides. In the presence of catalytic amounts of tertiary aliphatic amines yields as high as 90% are obtained. A series of adducts of mono-and di-phenols to mono- and bismaleinimides is described. Pure phenoxysuccinimides are stable compounds but the basic catalysts of their formation give rise to their decomposition into the phenolic component and oligomeric maleinimide. A nucleophilic reaction mechanism both for the formation and the decomposition is discussed. A new crosslinked addition polymer from a diphenol and a bismaleinimide with a surprisingly high heat stability is described.     

Über die Umsetzung von Thiazylfluorid mit mehrfunktionellen Stickstoffderivaten

Reaction of Thiazylfluoride with Multifunctional Nitrogen Derivatives From the reaction of NSF 1 with LiN(SiMe₃)R′ (R′ = CMe₃, SiMe₃), linear [e. g. (Me₃C? N?S?N? )₂S ( 11 ), Me₃C? N?S?N? CMe₃ ( 14 ), Me₃Si? N?S?N? SiMe₃ ( 17 ), (Me₃Si)₂N? S? N?S?N? SiMe₃ ( 19 )] and cyclic thiazenes (S₄N₅F ( 22 )) are isolated, (S₃N₄)_n ( 23 ) is obtained in high yield from 1 and 17 (in the ratio 2:1). Possible structures for 23 are discussed; the reaction of 23 with AsF₅ gives S₄N₄ · AsF₅ ( 24 ) in a hitherto unknown modification. Possible reactions of the terminal SN groups are discussed and the structures of 11 and 24 are reported.     

Über die Umsetzung von Adipinsäurediamid mit Phosphorpentachlorid

Reaction of Adipic Acid Diamide with Phosphorus Pentachloride The reaction of adipamide (I) with phosphorus pentachloride in a solvent leads to (Cl₃P?NCCl₂CCl₂CH₂)₂ (II). The stages of the reaction are: 1. chlorination of the keto and methylen groups 2. formation of the ? N?PCl₃ group. This result is a supplement of the existing conception about the course of the reaction of carboxylic acid amides with phosphorus pentachloride. The reaction of (I) with PCl₅ without any solvent has been reproduced and the course of reaction has also been investigated. This reaction gives mainly NC(CH₂)₄CN. The resulting product of a careful hydrolysis of (II) is (Cl₂OPN?CClCl₂CH₂)₂. A total hydrolysis gives back (I).     

Über die Reaktion von weißem Phosphor mit Jodwasserstoff

White phosphorus and hydrogen iodide quantitatively form PH₃ and P₂J₄ in anhydrous carbon disulfide. Besides PJ₃ the hitherto unknown iodophosphines PH₂J and PHJ₂ are formed during the reaction as intermediates.     

Über die Natur der Übergangsmetall-Kohlenstoff-σ-Bindung. VIII. Über die Reaktion von 3d-Metallhalogeniden mit Thioanisolyllithium

On the Nature of the Transition Metal Carbon-σ-Bond. VIII. Reaction of 3d-Metal Halides with Thioanisolyl Lithium Reaction of CoBr₂ · 2 THF with PhSCH₂Li/N(CH₂CH₂)₃N (TED) results in the formation of the thiophenolato complex LiCo(SPh)₃ · TED · 3.5 THF (I) with ethylene, propylene, and small amounts of cyclopropane being liberated. The constitution of I follows from the results of the elemental analysis, the effective magnetic moment (μ_eff. = 4.41 B.M.), and the reaction with acids and HgCl₂ to give PhSH and PhSHgCl, respectively. I could also be isolated by comparison synthesis from CoBr₂ · 2 THF and LiSPh/TED. Other 3d-metal halides MX_n · xTHF (M = Ti, V, Mn, Fe, Ni; X = Cl, Br) also react very easily with thioanisolyl lithium to form thiophenolato compounds.     

Über die Reaktion substituierter Thioxanthenoxide mit Säuren

9-[(N-Methyl-3′-piperidyl)-methyl]-thioxanthene-10-oxide (I) on treatment with boiling concentrated hydrochloric acid gives mainly 9-[(N-methyl-3′-piperidyl)-methylene]-thioxanthene (IV) together with small amounts of 9-[(N-methyl-3′-piperidyl)-chloro-methylene]-thioxanthene(II), 9-hydroxy-9-[(N-methyl-3′-piperidyl)-methyl]-thioxanthene (III) and 9-[(N-methyl-3′-piperidyl)-methyl]-thioxanthene (V). Treatment of I with acetic anhydride yields only IV.