Fluorenylsilane : III. Über die umsetzung von 9-fluorenyl-tris(trimethylsilyl)silan mit chlor

9-Fluorenyltris(trimethylsilyl)silane (A) reacts with chlorine in CCl₄ to give dichloro-9-fluorenyltrimethylsilylsilane (B) in good yield. B is characterized spectroscopically and by X-ray structure analysis; it crystallizes in the triclinic space group P$\text{1}$ with a 950(2), b 1367(3), c 1138(2) pm, α 137.5(1), β 109.9(2), γ 89.8(2)°. The conformation of B is staggered with approximate C_s-symmetry; C(9)Si 187.6(5), SiSi 233.2(4), SiCl 207.1(3) and 205.3(3) pm.     

Die Konstitution des Loroglossins. 163. Mitt. über organische Naturstoffe

The Constitution of Loroglossine Loroglossine, a characteristic constituent of orchids, is shown to be bis[4-(β-D -glucopyranosyloxy)-benzyl]-(2R, 3S)-2-isobutyl-tartrate (1) . Base catalysed hydrolysis and esterification with diazomethane gave 1 mol-equiv. of dimethyl (+)-2-isobutyl-erythro-tartrate ((+)- 3 ) and 2 mol-equiv. of a glucoside which after acetylation formed 4 identical with a synthetic sample. The structure of (+)- 3 follows from the synthesis of (±)- 3 by osmium tetroxide oxidation of isobutyl-maleic acid anhydride and subsequent esterification. The absolute configuration of (+)- 3 was based on Horeau experiments and NMR. data of the diastereomeric mixture of its esters 15 and 16 and pure 15 with (S)-(+)- and (R)-(?)-α-phenyl-butyric acid, respectively.     

Überblick über die Phosphide des Strontiums

The method of the reaction in a stainless steel cube which was used for the first time in the preparation of barium phosphides is also applicable to phosphide-producing mixtures of strontium and phosphorus. In connection with high temperature experiments it served to obtain a survey of the binary system strontium—phosphorus. This binary system is largely analogous to the binary system barium—phosphorus. The compounds found were: “Sr₂P”, Sr₃P₂, Sr₄P₃? Sr_1,1P, SrP, Sr₄P₅ and SrP². The strontium-rich phosphides have melting or decomposing temperatures which are higher than those of the analogous barium phosphides. The powders of Sr₃P₂, Sr₄P₃ and SrP are brown to blackviolet. Sr₃P₂ cristallizes isostructurally with Ba₃P₂. Some properties indicate that the bonding is more ionic than in Ba₃P₂. The structural relationship of the alkaline earth pnietides with the lanthanide chalogenides is discussed. Sr₃P₂ and Ba₃P₂ complete the inverse isostructures of these compounds.     

Notiz über die Photoelektronen-Spektren des Nortricyclens und des Triasterans

The photocelectron spectra of nortricyclene (=tricyclo[2.2.1.0^2,6]heptane) and of triasterane (=tetracyclo[3.3.1.0^2,8.0^4,6]nonane) have been recorded and a tentative assignment of the bands has been put forward on the basis of MINDO/2 SCF calculations.     

Untersuchungen über die Alkoholyse des SiS2. VI. Di-t-butoxysilandithiol

By alcoholysis of silicondisulphide the di-t-butoxysilanedithiol was obtained. This is the first compound with two SH groups bonded to silicon.     

Acetylenchemie 2. Mitt.: Sigmatrope Umlagerungen bei der phasentransferkatalysierten Umsetzung von 9(10H)-Acridinon mit 3-Chlor-3-methylbut-1-in

1-Isopropyl-pyrrolo[3,2,1-d,e]acridine-6-one and 10-(3,3-dimethylallenyl)-9(10H)-acridinone were obtained by the reaction of 9(10H)-acridinone with 3-chloro-3-methylbut-1-yne under ptc-conditions.

     

Anil-Synthese 22. Mitteilung über die Herstellung von Styryl-und Distyryl-Derivaten des Pyridins

Preparation of Styryl and Distyryl Derivatives of Pyridine 2,4-, 2,5- and 2,6-Dimethylpyridines react with anils of aromatic aldehydes in the presence of dimethylformamide and potassium hydroxide to yield the corresponding distyrylpyridines (‘anil synthesis’). Under the same reaction conditions (4-methylstyryl)pyridines are converted to (stilbenylvinyl)pyridines. Similarly, the Schiff's base derived from pyridine-3-carbaldehyde and p-chloroaniline on treatment with methyl- and p-tolyl-substituted aromatic heterocycles gives the corresponding (heteroaryl-styryl)pyridines, whereas with the Schiff's bases derived from pyridine-2- and -4-carbaldehyde side reactions, such as dimerization followed by disproportionation predominate.     

Untersuchungen über die Struktur von Formazanen I. 15N-H-Kopplung des Chelatwasserstoffatoms

¹⁵N-H-Coupling in 1, 3, 5-triphenylformazan derivatives demonstrates that these compounds are not resonance hybrids but tautomeric pairs. The position of the tautomeric equilibrium is a function of the substituents present in the phenyl nuclei on N-1 and N-5.     

Acetylenchemie, 14. Mitt.: PTC-Umsetzung von 9(10H)-Acridinon mit 3-Chlor-3-phenyl-1-propin und 3-Brom-1-phenyl-1-propin

Summary Reaction of 9(10H)-acridinone (2) with 3-chloro-3-phenyl-1-propyne under PTC conditions affords 1-methyl-2-phenyl-6H-pyrrolo[3,2,1-de]acridin-6-one (1 b), 10-(2-chloro-1-methyl-2-phenyl-ethenyl)-9(10H)-acridinone (4), 10-(3-phenyl-1-propynyl)-9(10H)-acridinone (7), and 10-(4-methylene-2,3-diphenyl-2-cyclobuteneylidenemethyl)-9(10H)-acridinone (5). The structure of the last compound which crystallizes in the triclinic system with the space group , was confirmed by X-ray diffraction. Under the same conditions 10-(3-phenyl-2-propynyl)-9(10H)-acridinone (3) and 10-(3-phenyl-1-propynyl)-9(10H)-acridinone (6) were obtained from 9(10H)-acridinone (2) and 3-bromo-1-phenyl-1-propyne.

     

Über die Si---N-bindung : XLIV. Die umsetzung von benzophenon mit bis- und tris(trimethylsilyl)amin

The thermal LiHal elimination of

- and

functional compounds provides a simple synthetic route to four-membered SiC and SiN rings. In attempts to inhibit dimerisation sterically, bulky silylmethyl and silylamino substituents were introduced (I–III). (Me₃Si)₃CSiF₂R reacts with LiNHR′, 1,3- migration of a silyl group from carbon to the nitrogen (I, R′= 2,4,6-Me₃C₆H₂) taking place. Substitution occurs for R′ = SiMe₂CMe₂, (II, III) only.Dichloro-bis(trimethylsilyl)methane reacts with halogenosilanes and lithium in THF to give bis(trimethylsilyl)-halogenosilaethanes (Me₃Si)₂CHSi(Hal)RR′; R= Me, R′ = N(SiMe₃)₂, IV, Hal = F; V, Hal = Cl. However a reductive THF cleavage accompanied by a silyl group migration to the oxygen occurs and 1-halogenosilyl-1- trimethylsilyl-5-trimethylsiloxi-pent-1-ene,(Me₃Si)(RR′SiHal)CCH(CH₂)₃OSiMe₃, Are The main products (VII–X) of these reactions. Disubstitution occurs with F₃Si-i-Pr (VI). (Me₃Si)₃CSiFNHSiMe₂CMe₃ (II) reacts with C₄H₉Li in a molar ratio $\text{1}\text{2}$ to give an 1-aza-2,3-disilacyclobutane (XI), involving substitution, LiF elimination, and nucleophilic migration of a methanide ion of the unsaturated precusor.(Me₃Si)₂CHSiFMeN (2,4,6-Me₃C₆H₂)SiMe₃ cyclizes under comparable conditions in the reaction with MeLi via a methylene group of the mesityl group (XII).     

Über die chemische Konstitution der mit Divinylsulfon vernetzten Cellulose. 12. Mitteilung über textilchemische Untersuchungen

Cotton and viscose fibres treated with divinyl sulphone under alkaline conditions were degraded in sulphuric acid. By column chromatography degradation products have been identified which contain two glucose units on mono- and dimeric sulphone derivatives, i.e. glucose ethers of 2,2′-dihydroxyethylsulphone and of 2,2′-bis-(hydroxyethylsulphonyl)-diethylether. This is the first direct chemical proof of the existence of cross-linkages in cellulose treated with bifunctional reagents.     

Spaltungen mittels Diazonium verbindungen und Chinonimidchlorid, 12. Mitt.: Über die Strukturzuordnung bei Azokupplungsprodukten des Resorcins

Zusammenfassung Es wird die Struktur der beiden möglichen isomeren Bis-(p-nitrobenzolazo)-resorcinverbindungen1 und4 mittels gezielter Azokupplung geeigneter Modellsubstanzen und durch NMR-spektroskopische Messungen festgelegt.

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The structures of the two possible isomeric bis(p-nitrophenylazo)-resorcinol derivatives1 and4 have been determined by diazo coupling of suitable model compounds and by n.m.r. spectroscopic studies.

     

Über die vierwertigen Verbindungen des Praseodyms, 4. Mitt.: Die thermische Dissoziation des Praseodymcarbonats

Zusammenfassung Bei der thermischen Dissoziation des Praseodym(III)-carbonats in Sauerstoffatmosphäre entsteht intermediär zuerst Praseodym(IV)-carbonat, welches sich bei wesentlich niedrigerer Temperatur (295–310°C) zersetzt als die Carbonate dreiwertiger Seltener Erden (>500°C). Daraus erklärt sich das anomale Verhalten des Praseodymcarbonats bei der thermischen Zersetzung.

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Thermal dissociation of praseodymium(III) carbonate in an atmosphere of oxygen yields as intermediate praseodymium(IV) carbonate which decomposes at much lower temperature (295–310°C) than the carbonates of the tervalent rare earths (>500°C). This explains the abnormal behaviour of praseodymium carbonate, when thermally decomposed.

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Mit 2 Abbildungen

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Vortrag bei der Tagung des Vereins Deutscher Chemiker in Bonn am 16. X. 1965.     

Magnetische Kernresonanz-Untersuchungen über die struktur der Komplexe aus Nitroaromaten mit azid-ionen 9. Mitteilung über nucleophile aromatische Subsitutionsreaktionen [1]

1. NMR. spectra of solutions of tetraethylammonium azide and 2,4,6-trinitro;benzene derivatives (methyl picrate, picryl chloride and picryl azide, respectively) demonstrate that the reactants probably form σ complexes.     

Untersuchungen über die Alkoholyse des SiS2. VIII Äthoxy-2,6-dimethylphenoxysilane

Studies on the Alcoholysis of SiS₂. VIII. Ethoxy-2,6-dimethylphenoxysilanes The reactions of 2,6-dimethylphenol and ethylalcohol with SiS₂ and SiCl₄ was investigated. Three new esters: ethoxy-2,6-dimethylphenoxysilanes were obtained.     

Über die Struktur eines neuartigen Indolalkaloids,des Talbotins. 141. Mitteilung über Alkaloide [1]

From the leaves of the African Apocynacea Pleiocarpa talbotii Wernham a novel indole alkaloid, talbotine, C₂₁H₂₄N₂O₄, has been isolated. Talbotine ( 1 ) contains a secondary N_(b)-atom and a cyclic hemiacetal group. Catalytic hydrogenation leads to 19, 20-dihydrotalbotine ( 6 ), hydrogenation in the presence of formaldehyde gives N_(b)-methyl-19, 20-dihydrotalbotine ( 8 ). In the presence of sodium methoxide and methanol, 1 is converted into the lactone 12 and the methyl ester 13 . In these reactions carbon 17 is lost as formic acid. These data, together with the analyses of the NMR. spectra of talbotine and its derivatives as well as the interpretation of the various types of the mass spectral fragmentation, lead to formula 1 for the alkaloid. Dehydrogenation of talbotine methyl ether ( 3 ) with palladium and maleic acid gives the ß-carboline derivative 26 . The N_(b)-methiodide of the latter is converted into N_(b)-methyl-talbotine methyl ether on reduction with sodium borohydride. From these data as well as from the analyses of NMR. and IR. spectra the complete relative stereochemistry of talbotine could be derived. Application of the Horeau method to the nitrogen atom b of the methyl ether 3 on the one hand and to the hydroxyl group on C17 in N_(b)-methyl-19, 20-dihydrotalbotine ( 8 ) on the other hand gives consistent results and establishes S configuration of centre 15.     

Über Chalkogenocarbonate. XLVIII. Untersuchungen über die lonen CS2Se2− und CSSe und über Kohlenstoffsulfid-hydrogensulfid-hydrogenselenid SC(SH)(SeH)

CS₂ forms with BaSe in aqueous solution the compound BaCS₂Se. The reaction of CSe₂ with BaS leads to mixed crystals of BaCSSe_a and BaCSe₃. The compounds were investigated by chemical, X-ray and IR-spectroscopical methods. Assignments of all normal vibrations of the ions CS₂Se^2- and CSSe were possible. The conductivity of CS₂Se^2- in aqueous solution was determine. By interaction of BaCS²Se with HCl the acid H₂CS₂SE (red oil) was prepared in form of its S, Se-protonated isomer; fast decomposition to H₂ Se and CS₂ occurs. From conductivity measurements it is concluded that the decomposition of H₂CS₂Se in aqueous solution is a first-order reaction via the anion HCS₂Se^?. Half-lifes and activation energy are given. The dissociation constants K_a1 and K_a2 were determind and thermodynamic data of the dissociation calculate. Date see ?Inhaltsübersicht”?.