Synthese und Eigenschaften einigerp-tolyl-phenylsubstituierter Di- und Trisilane und von 1,1,1,3,3,3-Hexaphenyltrisilan

The synthesis and properties of [Ph ₂ p-TolSi]₂, [Ph ₂ p-TolSi]₂SiPh ₂, [Ph ₃ Si]₂Si(p-Tol)₂, [Ph ₂ p-TolSi]₂Si(p-Tol)₂ and (SiPh ₃)₂SiH₂ are described. The silanes are identified using IR,Ra- and²⁹Si-NMR-spectroscopy.

     

Acyclische und cyclische Silylhydrazone und Hydrazonylsilane

Acyclic and Cyclic Silylhydrazones and Hydrazonylsilanes Dimethylketone-di-tert-butylmethylsilylhydrazone ( 1 ) is obtained in the reaction of the silylhydrazine and dimethylketone by condensation. Di-tert-butyldifluorosilane reacts with lithiated hydrazones to give fluorosilylhydrazones 2–4 , (CMe₃)₂SiF? NH? N = CRR′, ( 2 : R=Me, R′=CMe₃; 3 : R,R′=CHMe₂; 4 : R,R′=Ph). The bis(hydrazonyl)silane 5 , (CMe₃)₂Si(NH? N=CPh₂)₂, is formed in a molar ratio 1:2. Tris( 6 )- and tetrakis(hydrazonyl)silanes ( 7 ) are obtained from CMe₃SiF₃ ( 6 ), SiF₄ ( 7 ), and lithiated tert-butylmethylketon-hydrazone. The lithium derivatives 8–11 are formed in the reaction of 1–4 with butyllithium. Bis(silyl)hydrazones ( 12–15 ) are the result of the reaction of halogensilanes and the lithium derivatives of 1(8), 2(9) and 3(10); 12 : (CMe₃)₂SiMe(CMe₃SiF₂)-N? N=CMe₂, 13 : (CMe₃)₂MeSi(PhSiF₂)N? N=CMe₂, 14 : (CMe₃)₂SiF(Me₃Si)N? N=C(Me)(CMe₃), 15 : (CMe₃)₂SiF (SiMe₃)N? N=C(CHMe₂)₂. Saltelimination out of 10 und 11 leads to the formation of the first bis(imino)-2,2,4,4-cyclodisilazanes, 16 :[(CMe₃)₂ SiN? N=C(CHMe₂)₂]₂, 17 : [(CMe₃)₂SiN? N=CPh₂]₂. Cyclisation occurs in the reaction of 12 und 14 with tert-butyllithium, 2-silyl-1,2-diaza-3-sila-5-cyclopentenes ( 18 and 19 ) are formed. Dilithiated 1 reacts with SiF₄ to give the spirocyclic compound 20 . HF-elimination from 18 and dimerisation of the intermediate diazasilacyclopentadiens lead to the formation of the tricyclus 21 .     

Intra- und intermolekulare elektronische und Schwingungsrelaxation

Ohne Zusammenfassung     

Titan und Eisen in Titan-, Eisen- und Zirkoniumerzen und -konzentraten

Ohne Zusammenfassung     

Darstellung und strukturuntersuchungen von dimethylmetallacet- und acetimidohydrazinderivaten des galliums und indiums

Trimethylgallium and trimethylindium react with N′,N$\text{-}\text{?}$ dimethylacethydrazine and N′,N″,N′″-trimethylacetimidohydrazine, respectively, to form as a first step, monomeric dimethylmetal derivatives with five-membered ring skeletons. These heterocyclic compounds immediately add a further alkylmetal molecule. The ¹H NMR, IR and Raman spectra of these compounds are discussed and the results of X-ray structure determinations of two of the adducts are given.     

Nachweis und Bestimmung von Hydrastin und Berberin in Drogen und Extrakten

Ohne Zusammenfassung     

Physikalische und physikochemische Mikromethoden und -apparate

Ohne Zusammenfassung     

Herstellung und Charakteristika von o-Acryloyloxy- und o-Methacryloyloxybenzoes?ure und ihren Polymeren

Ohne Zusammenfassung     

Synthese und Charakterisierung von Fluorenylgallaten und Fluorenylindaten

Synthesis and Characterization of Fluorenyl Gallates and Fluorenyl Indates GaCl₃ reacts with Fluorenyllithium (LiFl) in the ratio 1:4 in Et₂O to [Li(THF)₄][GaFl₄] ( 1 ). The addition of DME (1,2-dimethoxyethane) to solutions of 1 in THF leads to [Li(DME)₃][GaFl₄] ( 2 ) under replacement of THF molecules by DME molecules in the coordination sphere of the Li⁺ ions. Treatment of InCl with LiFl in Et₂O and recrystallization from THF gives [Li(THF)₄][ClInFl₃] ( 3 ), which is formed by an disproportionation reaction. 3 can also be obtained by the reaction of InCl with FlZnCl/LiCl in Et₂O and recrystallization from THF. 1 and 2 crystallize from THF and THF/DME as [Li(THF)₄][GaFl₄] · THF ( 1 · THF) and [Li(DME)₃][GaFl₄] · THF ( 2 · THF), respectively. Crystalline 3 is isolated from the reaction of InCl and FlZnCl/LiCl, while the reaction mixture of InCl and LiFl gives after recrystallization in THF 3 · 1,5 THF. The gallate ions in 1 and 2 differ mainly in the position of the fluorenyl ligands. The unit cells of 3 and 3 · 1,5 THF contain two crystallographic unique ion pairs of [Li(THF)₄][ClInFl₃].     

Zur Anreicherung und Bestimmung von Platin und Palladium in Erzen und Konzentraten

Ohne Zusammenfassung     

Struktur und retentionsverhalten von offenkettigen und cyclischen kohlenwasserstoffen und deren einfacher substitutionsprodukte

Modern hydrocarbon and especially olefin chemistry is concerned with the stereospecificity of catalytic reactions. Mixtures resulting from these reactions must be analyzed for all possible isomers. Only gas chromatography with high resolution and mainly open tubular columns is able to separate the different isomers of unsaturated hydrocarbons present in such mixtures. The identidcation of the separated species is difficult, as the modern combination of mass spectroscopy with capillary columns supplies spectra which are not characteristic enough for identification of such unsaturated hydrocarbons. However, the interpretation of retention data of hydrocarbons may be successful, because small structural variations correspond to definite differences of retention data. The chemical history of the analyzed products and, in the case of methyl-substituted isomers, data on the methylene insertion reaction, make it possible to obtain a relative correlation of separated species.