1-Aryl- und 1-Alkyl-2-phthalimido-diazen-1-oxide,diacylierte Vertreter von trisubstituierten Triazen-1-oxiden: Bildung,Eigenschaften, Stereoisomerisierung und Fragmentierung

1-Aryl- and 1-Alkyl-2-phathalimido-diazene-1-oxides, Diacylated Examples of Trisubstituted Triazene-1-oxides: Formation, Properties, Stereoisomerization and Fragmentation¹) Oxidatively generated phthalimido-nitrene ( 1 ) reacts with nitrosobenzene ( 8a ), p-nitrosotoluene ( 8b ), o-nitrosotoluene ( 8c ), p-dimethylamino-nitrosobenzene ( 8d ), p-methoxycarbonyl-nitrosobenzene ( 8e ), 1, 1-dimethyl-1-nitrosoethane ( 8f ) and nitrosocyclohexane ( 8g ) to give the respective 1-substituted (Z)-2-phthalimidodiazene-1-oxides 14a-g . The constitution of 2-imidodiazene-1-oxides 14 is deduced from their spectroscopic properties. The UV. spectra of 14a-e are similar with those of the corresponding nitrobenzenes 18 , thus supporting the concept of comparibility of the phthalimido-N group with an O-atom and indicating that the phthalimido group is not in conjugation with the diazene-oxide function. This is in contrast to the situation in the non-acylated trisubstituted triazene-1-oxides 12 , where conjugation is extended over the chain of all three N-atoms as exhibited by the UV. spectra of (Z)-1, 3, 3-triphenyl-, (Z)-3, 3-dimethyl-1-phenyl-, (Z-3-methyl-1, 3-diphenyl-, (Z)-1-(1, 1-dimethylethyl)-3, 3-diphenyl-, and (Z)-1-(1, 1-dimethylethyl)-3, 3-dimethyltriazene-1-oxide ( 12a-e ). These triazene-1-oxides are formed by the reaction of 1, 1-disubstituted hydrazines 11 with three mol-equiv. of nitroso compounds 8 or from equimolar amounts of 11 and 8 in the presence of mercury oxide. Over 90% of 1, 2-diphenyldiazeneoxide ( 19 , R = C₆H₅) are isolated by the reaction 11 + 3 8a . Possible mechanisms of the reaction of 11 with 8 , and of the formation of 12 via triazanols D and of 19 (R = C₆H₅) via N-Phenylhydroxylamine ( 20 , R = C₆H₅) are given in Scheme 6 (in the latter case with experimental evidence). An independent synthesis of 12c confirms the constitutional assignment for 12 .     

Bildung,Eigenschaften und Strukturen von Bis(o-hydroxybenzylidenamin)

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Bildung, Eigenschaften und Strukturen von Bis(o-hydroxybenzylidenamin)

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Bildung und morphologische Eigenschaften von Schwefel an Viskosefasern

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Bildung und Eigenschaften von Acylphosphanen. V [1]. Tert. Butyl- und Phenylpivaloylphosphane

Synthese and Properties of Acylphosphanes. V. Tert. Butyl- and Phenylpivaloylphosphanes Synthese and properties of P-alkyl/arylmono and dipivaloylphosphanes are described using the tert. butyl and phenyl compounds as examples. Monopivaloylphoshanes are formed in the reaction of P-alkyl/arylpivaloyltrimethylsilylphosphanes (enol forms) with methanole and of P-alkyl/aryltrimethylsilylphosphanes or P-alkyl/arylmonolithiumphosphides with pivaloyl chloride; side reactions give 1,2-di(alkyl, aryl)-1,2-dipivaloyldiphosphanes. Tert. butylpivaloylphosphane is a rather stable compound; under the influence of light phenylpivaloylphosphane decomposes to pentaphenylcyclopentaphosphane, 2,2-dimethylpropionaldehyde, carbon monoxide and isobutane. With methyllithium P-alkyl/aryllithiumpivaloylphosphides are obtained, and subsequent reactions with pivaloylchloride yield P-alkyl/aryldipivaloylphosphanes. These compounds are also synthesized from P-alkyl/arylpivaloyltrimethylsilylphosphanes (enol forms) or P-alkyl/aryldilithiumphosphides and pivaloyl chloride.     

Synthesen mit Nitrilen, 17. Mitt.: Bildung und Eigenschaften von Bi-pyridonylen

Zusammenfassung Die Darstellung von Homologen des Bi-3-cyan-4-phenyl-2-pyridon-6-yls aus substit. Enaminoketonen und dimerem Malonitril wird beschrieben und der Reaktionsverlauf diskutiert. Abbauergebnisse liefern weitere Strukturbeweise.

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The synthesis of homologous Bi-3-cyano-4-phenyl-2-pyridon-6-yls from substituted enaminoketones and dimeric malonitrile is given and the reaction discussed. Hydrolysis brings additional proof of structure.

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Synthese von in 2-Stellung substituierten 2-Amino- und 3-Amino-1-indanonen

An examination has been made of the reaction of secondary amines with 2-bromo-1-indanones II substituted at position C-2, and with 2-substituted indenones III. 2-Bromo-2-methyl-1-indanone (IIa) and dimethylamine yielded a mixture of the corresponding 2- and 3-amino-methylindanones IVa and Va. 2-Bromo-2-methyl-6-chloro-1-indanone (II b) and morpholine gave a mixture of the 2- and 3-aminocompounds IVe and Ve.     

Bildung der Poly-p-xylylen-Filme aus der Gasphase und Untersuchung ihrer Eigenschaften

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Beiträge zur Chemie der Enaminoketone, 3. Mitt.: Darstellung und Eigenschaften neuer 3-Amino-1-phenylpropenone

Zusammenfassung Die Reaktion von 3-Dimethylamino-1-phenyl-propenon mit 2-Aminothiazol, 2-Aminopyridin, 3-Aminopyridin und 2-Aminopyrimidin verläuft unter Abspaltung von Dimethylamin zu den heterocyclisch substituierten Enaminoketonen3, 4, 5 und6. Diese Verbindungen liegen bei Raumtemperatur überwiegend in dercis-Form vor, nur im Thiazolylamino-tolyl-propenon (3) herrscht dietrans-Form vor.

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Enaminoketones, III.: Preparation and properties of some novel 3-amino-1-phenylpropenones

Reaction of 3-dimethylamino-1-phenyl-propenone with 2-aminothiazol, 2-aminopyridine, 3-aminopyridine and 2-aminopyrimidine, resp., proceeds with the elimination of dimethylamine to give the heterocyclic enaminoketones3, 4, 5, and6, resp. At room temperature thecis-form of these compounds predominates; only thiazolylaminotolylpropenone3 exists in thetrans-form.

     

Na2C2 und K2C2: Synthese,Kristallstruktur und spektroskopische Eigenschaften

Na₂C₂ and K₂C₂: Synthesis, Crystal Structure, and Spectroscopic Properties By the reaction of sodium or potassium solved in liquid ammonia with acetylene and subsequent heating in high vacuum Na₂C₂ and K₂C₂ could be synthesised as single phase products. The crystal structures described by Föppl could be confirmed by X-ray and neutron diffraction experiments (K₂C₂) on powdered samples. Both compounds crystallise in a tetragonal structure (I4₁/acd, no. 142, Z = 8) which can be described as a distorted variant of the antifluorite-structure type. At temperatures above room temperature (Na₂C₂: 580 K, K₂C₂: 420 K) a reversible phase transition (1^st order transition) to a cubic modification (Fm 3 m, no. 225, Z = 4) has been observed, analogous to the alkaline earth metal acetylides. This high temperature modification represents an undistorted antifluorite structure with disordered C₂^2– dumbbells. The results of raman- and ¹³C-MAS-NMR-spectroscopic investigations are in agreement with acetylide dumbbells in the title compounds and allow a comparison to the respective monoalkalimetal and alkaline earth metal acetylides.     

Fluorkomplexe des Siliciums in wäßriger Lösung, 2. Mitt.: Bildung und Eigenschaften der Tetrafluorokieselsäure

The SiF₄ partial pressures of strongly acidified fluorosilicate solutions has been measured as a function of various parameters (Si:F ratio, total concentration of fluorine, water activity, acidity, temperature). The experimental data provide information on formation and properties of the silicon tetrafluoro complexes. Tetrafluorosilicon complexes are formed in high yield when hexafluorosilicate solutions are saturated with silica at high acid concentrations. They contain 2 moles H₂O per mole SiF₄; their formula can be written as SiF₄·2 H₂O. Silicon tetrafluoride dihydrate behaves like a strong acid. As to be expected, it is less stable than the corresponding ammonia adduct.     

Bildung und elastische Eigenschaften der Netzwerke, die aus Methacryls?ure estern hergestellt wurden

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CsC2H: Synthese,Kristallstruktur und spektroskopische Eigenschaften

CsC₂H: Synthesis, Crystal Structure, and Spectroscopic Properties CsC₂H was synthesised by the reaction of caesium solved in liquid ammonia with acetylene. The crystal structure could be solved and refined from X‐ray and neutron powder diffraction data (space group: R3c, Z = 18). The structure is characterised by C₂H^– trimers which are surrounded by caesium ions. Spectroscopic investigations (IR and Raman) of the stable monoalkalimetal acetylides mainly confirm the data given in the literature and show that the alkalimetal cation has a marked influence on the vibrational properties of the C₂H^– anion.     

Bildung und Eigenschaften von Aoylphosphinen. III. Molekül- und KristallStruktur von Dipivaloylphosphin

Syntheses and Properties of Acylphosphines. III. Molecular and Crystal Structure of Dipivaloylphosphine In the reaction of tris(trimethylsilyl)phosphine with pivaloyl chloride two Si? P bonds are cleaved and dipivaloyltrimethylsilylphosphine is formed. Reaction with methanol yields dipivaloylphosphine. N.m.r. investigations show a tautomeric equilibrium between keto and enol form as in β-diketones. The substance crystallizes in the orthorhombic space group Pmmn with molecules in two crystallographically different sites [cell parameters: a = 14.04(1), b = 13.82(1), c = 6.28(2) Å]. An X-ray structure determination (R = 5.0%) proves the existence of the enol form in the solid, in that (1.) the molecular symmetry is mm 2(C_2v), (2.) P? C bonds are shortened and C? O bonds are elongated, and (3.) we find a symmetric hydrogen bridge with a very short O? O distance. Bond lengths and angles are compared with those of other β-diketones. The packing of molecules is studied in detail.