Zur Reaktion von Polyvinylchloridpolymeren mit Pyridin

Zusammenfassung Die Wechslersche Reaktion auf Polyvinylchloridpolymere (PVC) mit Pyridin, durch die in Gegenwart methanolischer Natronlauge auftretende Braunschwarzfärbung der Lösung gekennzeichnet, daher aber nur im Rahmen dieser Bedingungen charakteristisch, beruht auf einer Reihe von Spaltungsvorgängen, die, wie wahrscheinlich gemacht werden konnte, zum Teil zum Glutacondialdehyd (Natriumenolat) als Zwischenprodukt führen. Dadurch ist zugleich eine Verschärfung des PVC-Nachweises möglich, indem man den Glutacondialdehyd in saurer Lösung mit -Naphthylamin kondensiert, den entstandenen Pentamethinfarbstoff mit Amylalkohol extrahiert und dessen Umschlag von Rot nach Gelb und wieder nach Rot mit Lauge und Säure zur weiteren Charakterisierung heranzieht.     

Zur Reaktion von Silber mit Kohlendioxid

On the Reaction of Silver with Carbon Dioxide Mechanical activation of metallic silver in a CO₂ atmosphere was shown to oxidize the silver. The resulting monovalent silver was found by a wet chemical procedure to be made up of Ag⁺ ions, while the Ag₂CO₃ was determined from Debye-Scherrer patterns. During mechanical treatment CO₂ and the CO formed are absorbed within the solid. The reaction equation 2 Ag + 2 CO₂ ← Ag₂CO₃ + CO is suggested for the reaction, giving a positive free enthalpy of 212 kJ/mol. This high amount of energy is locally supplied during the mechanical treatment of the metallic silver.     

Zur Reaktion von Halogenwasserstoffen mit Phenyldisilanen

The removal of phenyl groups from disilane derivatives with HCl and HBr to form silicon-halogen bonds has been studied in a variety of methylphenyldisilanes to establish the possible range of application. Besides the preparation of several new compounds, a convenient method is described for the synthesis of certain disilane derivatives which have until now been accessible only with difficulty.     

Zur Reaktion von Triphenylphosphan mit Thionylchlorid

Triphenylphosphine reacts with thionyl chloride to give [Ph₃PCl]Cl, Ph₃PO and Ph₃PS the formation of the anions S(O)Cl and SCl being discussed; the crystal structure of [Ph₃PCl]Cl · S(O)Cl₂ is reported.     

Zur Reaktion von Chloraceton mit Phenylhydrazin

The first product identified from the reaction of chloroacetone (1) with phenylhydrazine is 2-phenylazo-propene (2). Two further isolated products are methylglyoxal bisphenylhydrazone4 and the addition product of4 and2, its structure6 has been derived from spectroscopic data (¹H-nmr and uv).

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1. Mitt. über Additionsprodukte von Hydrazinderivaten an Azoolefine.     

Zur Reaktion von Permethylcyclosilanen mit Halogenen

The series of ,-diiodopermethylpolysilanes, I(SiMe ₂) _n I, (n=4–6) andX(SiMe ₂)₄ X, (X=Cl, Br) has been prepared by the action of halogen on the corresponding cyclic compounds (SiMe ₂) _n . The mass spectra, NMR-, IR- andRaman-spectra of these compounds have been recorded.

Herrn Prof. Dr.Josef Schurz zum 60. Geburtstag gewidmet.     

Zur Reaktion von Chlorsilanen mit Dialkylphosphonaten

Summary The reaction of dichlorodiorganosilanes with dialkylphosphonates is described. Depending on the reaction conditions diorganosilyl-bis(O-alkylphosphonates)R ₂Si[OP(O)H(OR)]₂ and diorganosilylphoshonates [-R₂Si-OP(O)HO-], respectively, are formed.Using this type of reaction, O-alkoxysilyl O-alkylphosphonates can be obtained both by interaction of dialkylphosphonates with dichlorodialkoxysilanes or chlorodialkoxyalkylsilanes, respectively.

Herrn Professor Dr. E. Hengge anläßlich seines 60. Geburtstages gewidmet     

Zur Reaktion von Imidodiphosphoryltetrachlorid mit Phosphorpentachlorid

Reaction of Imidodiphosphoryl Tetrachloride with Phosphorus Pentachloride Imidodiphosphoryl tetrachloride quantitatively reacts with PCl₅ to form, HCl, POCl₃, and Cl₃P?N? POCl₂. The mechanism of the reaction is discussed. Using ³²P-labeled PCl₅ was proved that the attack of the PCl₅ to imidodiphosphoryl tetrachloride does occur about an oxygen atom.     

Zur Reaktion von Diketen mit Keton-anilen

Zusammenfassung Die Umsetzung von Diketen (1) mit Cyclanonanilen (2) gibt als Hauptprodukte 5.6-Polymethylen-4-pyridone (5) neben, geringen Mengen von 4-Pyronderivaten (4). Bei der Umsetzung von1 mit Aralkylketonanilen6 entstehen, außer den entsprechenden 4-Pyridonen8 beträchtliche Mengen an 1-Phenyl-1.5-bis-(phenylamino)-1.4-hexadien-3-onen (7), welche beim Erhitzen mit HCl Ringschluß zu8 erleiden. Benzoylessigester (9) reagiert mit1 zum 3-Acetyl-4-hydroxy-6-phenyl-2-pyron (11).

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Syntheses of heterocycles, CLIII: Reaction of diketene with ketone aniles

The reaction of diketene (1) with cyclanone aniles (2) gives mainly 5.6-polymethylene-4-pyridones (5) besides some 4-pyrone derivatives (4). The action of1 on aralkyl ketone aniles (6) yields the corresponding 4-pyridones (8), and a considerable amount of 1-phenyl-1.5-bis-(phenylamino)-1.4-hexadien-3-ones (7). The latter undergo ring closure (with HCl) affording the 4-pyridones (8). Diketene (1) reacts with ethyl benzoylacetate (9) yielding 3-acetyl-4-hydroxy-6-phenyl-2-pyrone (11).

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Aus der DissertationI. Herbst, Universität Graz, Februar 1968.     

Zur Reaktion von Trifluorhalomethanen mit Phosphanen

On the Reaction of Trifluorohalomethanes with Phosphanes The reactions of trifluorohalomethanes CF₃X (X = Cl, Br, I) with Ph₃P, Bu₃P, (Me₂N)₃P, and (Et₂N)₃P were investigated. CClF₃ does not react. In the reactions of CBrF₃ and CF₃I with Bu₃P in acetonitrile trifluorophosphonium salts, [Bu₃PCF₃]X (X = Br, I), are formed, whereas gaseous CF₃I and Bu₃P yield Bu₂PCF₃. Depending on the reaction conditions the aminophosphanes form either [(R₂N)₃PX]X (R = Me, Et; X = Br, I) and CF₃H or [(R₂N)₃PCF₃]X.     

Zur Reaktion von Fluorphosphanen mit Silylaziden

On the Reaction of Fluorophosphanes with Silylazides . The fluorophosphanes Ph₂PF ( 1 ), PhOPF₂ ( 2 ), C₅H₁₀NPF₂ ( 3 ), (Et₂N)PF₂ ( 4 ), and (Et₂N)₂PF ( 5 ) react with Me₃SiN₃ via azidophosphanes R_3?nP(N₃)_n to oligo- and polyphosphazenes, (RR′P?N)_n. (ⁱPr₂N)₂PF ( 6 ), however, is oxidized by Me₃SiN₃ yielding the N-silylated phosphazene (ⁱPr₂N)₂PF?N? SiMe₃ ( 7 ). ^tBuPh₂SiN₃ is considerably less reactive. On contrary to Me₃SiN₃ it even oxidizes 5 and 1 forming (Et₂N)₂FP?N? SiPh₂^tBu ( 10 ) and Ph₂FP?N? SiPh₂^tBu, resp.     

Zur Reaktion von metallischem Natrium mit Stickoxid-Gas

Zusammenfassung Es konnte festgestellt werden, daß bei Reaktionstemperaturen zwischen 190° und 230°C keine direkte Addition von Stickoxid-Gas an metallisches Na unter Bildung von Nitrosylnatrium. NaNO, stattfindet. Vielmehr konnte gezeigt werden, daß die Reaktion analog der von Natriumoxid mit Stickoxid-Gas unter Bildung von Natriumnitrit. Natriumhyponitrit, Natriumoxid und geringer Mengen Natriumdioxonitrat (II) (Natriumhydronitrit) abläuft.Mit 2 AbbildungenVon diesem Institut Herrn Prof. Dr.O. Kratky. Graz. zum 60. Geburtstag gewidmet.     

Zur Reaktion von Fluorsilanen mit lithiierten Aminen

The reaction of fluorosilanes with lithium salts of bulky amines like tetramethyl-piperidine and di-tert. butylamine leads to stable aminofluorosilanes of the type R-SiF₂-NRR [R=F, C(CH₃)₃, C₆H₅, C₆H₄N(CH₃)₂]. Lithium salts of silylamines react analogously: R₂Si(NR-SiF₂R)₂ (R=R= =CH₃, R=C₆H₅). An eight membered Si–N-ring is obtained in the reaction of a disubstituted silylaminofluorosilane with the dilithium salt of a silylamine. The mass-,¹H-, and¹⁹F-NMR spectra of the above mentioned compounds are reported.     

Zur Reaktion von Aluminium mit Schwermetallchloriden in Salzschmelzen

On the Reaction of Aluminium with Heavy Metal Chlorides in Molten Salts The conversion of aluminium in an equimolar AlCl₃—NaCl melt with heavy chlorides (PbCl₂, CdCl₂, CuCl₂) to AlCl₃ is effected in the temperature range of 620—780 K according to the time-concentration course as a reaction of first order. From the temperature dependence the apparent activation energies have been calculated. They are in the order of magnitude of the activation energies for the diffusion of the corresponding metal ions in molten salts.     

Zur Reaktion von Dichlorphenylboran mit Nitridokomplexen des Rheniums

The Reaction of Dichlorophenylborane with Nitrido Complexes of Rhenium BCl₂Ph reacts with terminal nitrido ligands of rhenium complexes under formation of a nitrogen bridge between the transition metal and boron. Structural studies on [Re(NBCl₂Ph)Cl₂(Ph₃P)₂], [Re(NBCl₂Ph)Cl₂(Me₂PhP)₃], [Re(NBCl₂Ph)Cl(Me₂PhP)₂(Et₂dtc)] and [Re(NBCl₂Ph)(Me₂PhP)(Et₂dtc)₂] (Et₂dtc^– = N,N′‐diethyldithiocarbamate) demonstrate that the rhenium‐nitrogen bond is only slightly lengthened upon the formation of the nitrido bridge whereas a significant decrease of the structural trans influence of the nitrido ligand is observed. [Re(NBCl₂Ph)Cl₄(Y)]^– (Y = Cl or solvent) complexes are formed during the reaction of [ReNCl₄]^– with BCl₂Ph. The rhenium(VI) compounds (d¹configuration) can easily be detected by EPR spectroscopy. The formation of {Re(NBCl₂Ph)} complexes with mixed Cl^–/Br^– (or NCS^–) coordination spheres is evident when the reactions start from [ReNBr₄]^– or [ReN(NCS)₅]^2– which can be derived from the EPR spectra of the reaction mixtures.     

Zur Bildung von Difluorhalogenmethylarsanen durch Reaktion von Difluorcarben mit Arsenhalogeniden

Formation of Difluorohalomethyl Arsanes by Interacting Difluorocarbene with Arsenic Halides Bis(trifluoromethyl)cadmium stabilized by acetonitrile, Cd(CF₃)₂ · 2 CH₃CN, is used as source for the in situ formation of difluorocarbene. Difluorocarbene reacts with arsenic halides, AsX₃ (X = Cl, Br, I) to form the corresponding difluorohalomethylarsanes, As(CF₂X)_nX_3?n. The extent of insertion increases in the series AsCl₃ < AsBr₃ < Asl₃. The cadmium complex behaves towards AsF₃ as trifluoromethylating agent.     

Zur Reaktion von 1,4-Pentadien-3-onen mit Phenylacetonitrilen

Diarylpentadienones (1) react with phenylacetonitriles (2) to give 4-oxo-1.2.6-triaryl-cyclohexane-1-nitrils (4). Isomer compounds (6) may be obtained byMichael addition of2 to esters of cinnamic acids and cyclisation to5, followed by hydrolysis and decarboxylation. The steric behaviour of4 and6 is established by¹H- and¹³C-NMR-spectroscopy and by the different mode of reaction and products in the condensation of4 and6 with aromatic aldehydes to give8 or9.     

Zur Reaktion von Hydroxy- und Amino-pyridinen mit reaktiven Malonestern

Zusammenfassung Das Verhalten der Hydroxy- und Amino-pyridine gegenüber Malonsäure-bis-2,4,6-trichlorphenylestern (1) wird untersucht. Im besonderen werden die Reaktionen des 3-Hydroxy-pyridins (4) mit1 zu 4-Hydroxy-2H-pyrano[3,2-b]pyridin-2-onen (5 a-e) und die des 2-Amino-3-hydroxy-pyridins (15) zu 2,9-Dihydroxy-4H-pyrido[1,2-a]pyrimidin-4-onen (16 d-f) beschrieben.

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Syntheses of heterocycles, CLX: the reaction of hydroxy and amino pyridines with reactive malonic esters

The reaction of hydroxy and amino pyridines with 2.4.6-trichlorophenyl malonates (1) is discussed. Especially the reaction of 3-hydroxy-pyridine (4) with1 to 4-hydroxy-2H-pyrano[3.2-b]pyridine-2-ones (5 a-e), and the reaction of 2-amino-3-hydroxy-pyridine (15) to 2.9-dihydroxy-4H-pyrido-[1.2-a]pyrimidin-4-ones (16 d-f) is described.

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Herrn Prof. Dr. Dr. h. c.O. Kratky, Vorstand des Institutes für Physikal. Chemie der Universität Graz, zum 70. Geburtstag gewidmet.