Darstellung und Eigenschaften von Carbonylisocyanat

Zusammenfassung Es wird über die erstmalige Darstellung von Carbonylisocyanat, CO(NCO)₂, durch thermische Zersetzung von Trichlorisocyanursäure berichtet; einige physikalische Eigenschaften der neuen Verbindung werden mitgeteilt. Ihre Reaktionen mit Alkali, Wasser, Ammoniak und Äthanol wurden untersucht. Durch Reaktion mit Wasser im Verhältnis 1: 1 wurde 2,4,6-Trioxo-tetrahydro-1,3,5-oxadiazin bzw. Carbonyldicarbamidsäureanhydrid als neue Verbindung erhalten.

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Carbonyl isocyanate has been prepared the first time by thermolysis of trichlorisocyanuric acid and some of its physical properties have been determined. Its reactions with alkali, water, ammonia and ethanol have been investigated. By reaction with equimolar amounts of water the novel compound 2,4,6-trioxotetrahydro 1,3,5-oxadiazine (carbonyl-dicarbamic acid anhydride) was obtained.

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Auszugsweise vorgetragen auf der Vortragstagung des VOeCh. am 28. 9. 1965 in Graz.     

Darstellung und Eigenschaften von Trifluormethylmercaptothiophosphoryldichlorid

Preparation and Properties of Trifluoromethylmercaptothiophosphoryldichloride The reaction of CF₃SP(O)Cl₂ with SPCl₃ leads to a CF₃S-chlorine exchange and gives CF₃SP(S)Cl₂ in 50% yield. A controlled hydrolysis of CF₃SP(O)Cl₂ affords CF₃SP(O)(OH)₂, that cannot be isolated as such, but it condenses to CF₃SP(O)(OH)O? [P(SCF₃)(O)? O]_nP(O)(OH)SCF₃. On the other hand, CF₃SP(S)Cl₂ reacts with water to yield H₃PO₄, CF₃SH, S₈, and HCl. CF₃SP(X)Cl₂ reacts with alcohols to give CF₃SP(X)(OR)₂ [R = CH₃, C₂H₅, n-C₃H₇, CH(CH₃)₂, n-C₄H₉ and for X = O, R = C₆H₅, too]. The formation of semi-esters CF₃SP(X)Cl(OR′) could be proven for X = O, R′ = CH₃, C₆H₅ and for X = S, R′ = R. While CF₃SP(O)(OC₂H₅)₂ rapidly decomposes into SCF₂ and FP(O)(OC₂H₅)₂, the other compounds and primarily CF₃SP(O)(OCH₃)₂ and CF₃SP(S)(OR)₂ ar stable. The reaction between CF₃SCl and CH₃SPCl₂ results in CF₃SCH₂SPCl₂ and that between CF₃SP(O)Cl₂ and AlCl₃ gives [CF₃SP(O)Cl]⁺[AlCl₄]^?. Physical and spectroscopical data are given for the newly formed compounds.     

Darstellung und Eigenschaften von Phenyljodcyclopentasilanen

Zusammenfassung Dekaphenylcyclopentasilan reagiert mit wasserfreiem HJ im Bombenrohr unter Benzolabspaltung zu Phenyljodcyclopentasilanen. Der Grad der Phenylabspaltung hängt von der Reaktionszeit ab. Reaktion mit Methanol führt zu entsprechenden Methoxyphenylcyclopentasilanen.Die Hydrolyse ergibt gelbe, fluoreszierende, polymere Hydrolysenprodukte, in denen Si₅-Ringe über Sauerstoff verknüpft sind. Die Farbe der Hydrolysenprodukte wird im Zusammenhang mit den Ergebnissen der Siloxenchemie diskutiert.

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Synthesis and properties of phenyliodocyclopentasilanes

Decaphenylcyclopentasilane reacts with anhydrous HJ in a sealed tube to give phenyliodocyclopentasilanes and benzene, and the degree of phenyl cleavage was found to depend on the reaction time. The corresponding methoxyphenylcyclosilanes are obtained in the reaction with methanol. Hydrolysis yields a yellow, fluorescent, polymeric compound containing Si₅-rings coupled by oxygen. The colour of the hydrolysis products is discussed in connection with pertinent results in siloxene chemistry.

     

Darstellung und Eigenschaften von Organoindiumbromiden

Synthesis and Properties of Organoindium Bromides i-Pr₃In gives with InBr₃ (molar ratio 2:1, toluene, 50°C) i-Pr₂InBr ( 1 ) and (molar ratio 1:2, toluene, 80°C) i-PrInBr₂ ( 2 ). The corresponding reaction of (PhCH₂)₃In and InBr₃ (2:1) gives (PhCH₂)₂InBr ( 3 ), while PhCH₂InBr₂ could be isolated only as ether adduct [PhCH₂InBr₂(OEt₂)_n] ( 4 ). With DME/MeCN and 2 and 4 with THF, respectively, yields the solvate complexes [InBr₃(DME)(MeCN)] ( 5 ), [i-PrInBr₂(THF)₂] ( 6 ) and [PhCH₂InBr₂(THF)₂] ( 7 ). The compounds 1–7 were investigated with NMR-, IR- and MS-techniques. Pyrolysis of the raw material of i-Pr₃In, which contains “MgBrCl” and additional treatment with Et₂O yields the salt [Mg₃Cl_4,65Br_0,35(Et₂O)₆][i-PrInBr_2,7Cl_0,3] ( 8 ). The cation, a trinuclear magnesium complex, possesses local D_3h-symmetric of the Mg₃X₅ backbone (X = Cl, Br).     

Darstellung und Eigenschaften von Bromisocyanat

Zusammenfassung Durch Vakuumthermolyse von Tribromisocyanursäure konnte Bromisocyanat in größeren Mengen dargestellt werden. Eine genauere Charakterisierung der bereits an anderer Stelle beschriebenen Verbindung sowie ein Vergleich mit den Eigenschaften von Chlorisocyanat werden gegeben.

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Preparation and properties of bromo isocyanate

Bromo-isocyanate has been prepared by vacuum thermolysis of tribromo-isocyanuric acid. A more exact characterization of this just elsewhere described compound and a comparison with chloro-isocyanate are given.

     

Darstellung und Eigenschaften von Aminodisilanen

Zusammenfassung Aus der Klasse der teilweise substituierten Aminodisilane wurden vier Vertreter der Dimethylaminomethyldisilane erstmals hergestellt und durch Analyse, Molrefraktion, UV-,¹H-NMR-, IR- und Ramanspektren charakterisiert.

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Preparation and properties of amino disilanes

Four dimethylamino-methyldisilanes have been prepared and characterized by analysis, molar refraction, UV,¹H-NMR, IR and Raman spectra.

     

Darstellung und Eigenschaften von Trinorbornylbor-Verbindungen

Synthesis and Properties of Trinorbornyl Boron Compounds Tris(1-norbornyl), Tris(2-norbornyl), and Tris(7-norbornyl) boron were synthesized from boron trifluoride diethylether and 1-norbornyl lithium or 2- and 7-norbornyl magnesium halides respectively. The compounds were characterized by the IR-, ¹³C-, ¹¹B-NMR, and mass spectra. Furthermore 1-norbornyl lithium was isolated in the crystalline state and investigated in detail.     

Darstellung und Eigenschaften von Chlorisocyanat

Zusammenfassung Die Darstellung von Chlorisocyanat durch Vakuum-Thermolyse von Trichlor-isocyanursäure wird beschrieben, einige physikalische Eigenschaften der neu dargestellten Verbindung werden mitgeteilt. Ihre Reaktionen mit Wasser, Alkali, Ammoniak und Äthanol werden untersucht. An Hand des IR-Spektrums werden Aussagen über die Struktur der Verbindung gemacht.

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Chloro-isocyanate has been prepared for the first time by vaccum thermolysis of trichloro-isocyanuric acid; some of its physical properties have been determined. Its reactions with water, alkali, ammonia and ethanol have been investigated. Based on the infrared spectrum of the novel compound, the molecular structure is discussed.

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Mit 1 Abbildung

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Auszugsweise vorgetragen auf der Vortragstagung des VÖCh am 28. Sept. 1965 in Graz.     

Darstellung und Eigenschaften von Norbornylquecksilberverbindungen

Preparation and Properties of Norbornyl Mercury Compounds Bis(1-norbornyl) and bis(2-norbornyl)mercury, 1- und 2-norbornylmercury chloride and 1-norbornylmercury i-butyl were synthesized and characterized by ¹³C-N.M.R. investigations and in case of bis(1-norbornyl) mercury also by the I.R. and mass spectrum. The ¹J(¹⁹⁹Hg? ¹³C) coupling constants of the 1-norbornyl compounds demonstrate the trans-influence of the norbornyl anion.     

Darstellung und Eigenschaften von Methyl-methoxydisilanen

Zusammenfassung Methoxymethyldisilane werden durch Alkoholyse von Chlormethyldisilanen, bzw. durch Reaktion von Methoxychlorsilanen mit Trimethylsilyllithium hergestellt und näher charakterisiert. Auch bei diesen Verbindungen zeigt sich der schon früher beschriebene Einfluß des Sauerstoffs auf die Si–Si-Bindung, die durch die zusätzliche Elektronenbelastung des Siliciums durch die Elektronen des Sauerstoffs verstärkt wird.

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Methoxy methyl disilanes where prepared by means of alcoholysis of chloromethyl disilanes, or by reaction of methoxy chlorosilanes with trimethyl silyl lithium. These compounds also exhibit the already described influence of the oxygen upon the Si–Si bonding, which results in a strengthening of the bond by the electrons made available through the oxygen.

     

Darstellung und Eigenschaften von Tetracyanmethan

Zusammenfassung Tricyanmethylsilber reagiert mit Chlorcyan unter Bildung von Tetracyanmethan und AgCl. Das erstmals beschriebene Tetracyanmethan ist kristallin, sublimiert bei 60° im Vak., zersetzt sich ab 160° und ist in polaren Lösungsmitteln löslich. Das IR-Spektrum wird diskutiert und eine Zuordnung der Normal-schwingungen für T_d-Symmetrie getroffen. Die Hydrolyse in saurem und alkalischem Medium und die Reaktion mit LiCl werden beschrieben.

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Preparation and Properties of Tetracyanomethane

The reaction of silver tricyanomethanide with cyanogen chloride yields the hitherto unreported tetracyanomethane and AgCl. Tetracyanomethane is a crystalline solid, sublimes at 60° in vacuo, decomposes above 160° and is soluble in polar solvents. The IR spectrum is discussed and an assignment of the fundamental frequencies based on T_d symmetry is made. Hydrolysis with acid or alkali and the reaction with LiCl are described.

     

Darstellung und Eigenschaften von Ti-substituierten N-Heterocyclen

Preparation and Properties of Ti-substituted N-Heterocycles The compounds (x = 2 to 6) have been prepared by transamination of Ti(NMe₂)₄ with the heterocyclic amines and have been characterised by elemental analyses and ¹H NMR and IR spectroscopy. The dependence on both x and n of the thermal decomposition has been studied for the series and . The results can be interpreted in terms of the steric strain of the R₂N and substituents. Apart from the piperidido groups none of the ligands exhibit protective group properties comparable to the R₂N groups.     

Darstellung und Eigenschaften von 1-Norbornylkupfer

Preparation and Properties of 1-Norbornyl Copper 1-Norbornyl copper was synthesized from copper(II) acetylacetonate and 1-norbornyl lithium. The compound shows an unexpected stability and decomposes only at ca. 80°C with precipitation of copper and formation of norbornyl radicals which were proved by spin-trap experiments. A further characterization was performed by the IR and ¹³C-NMR spectra.     

Darstellung und chemische Eigenschaften von N-Trifluormethylthiophosphaniminen

Preparation and Chemical Properties of N-Trifluoromethylthiophosphaneimines In n-hexane (CF₃S)₃N and (C₆H₅)₃As react to CF₃SN?As(C₆H₅)₃ and CF₃SSCF₃. With (RO)₃P (CF₃S)₃N forms CF₃SSCF₃ and CF₃SN?P(OR)₃ (R = C₆H₅, CH₃, C₂H₅). While CF₃SNP-(OC₆H₅)₃ is stable up to 100°C the other Phosphaneimines rearange to (R′O)₂P(O)N(R′)SCF₃ (R′ = CH₃, C₂H₅). Hydrolysis leads to ROH and (RO)₂P(O)N(H)SCF₃. Only for R = C₆H₅ in addition (C₆H₅O)₂P(O)NH₂ is formed. Physical data and nmr spectra of the newly prepared substances are presented.     

Darstellung,Kristallstruktur und Eigenschaften von Kaliumhydrogencyanamid

Preparation, Crystal Structure, and Properties of Potassium Hydrogen Cyanamide For the preparation of KHCN₂ melamine has been reacted with potassium amide in liquid ammonia. After evaporation of the solvent the resulting solid has been transformed at 210°C. KHCN₂ (P2₁2₁2₁, a = 708.7(2), b = 909.0(2), c = 901.4(2) pm, Z = 8, R = 0.039, wR = 0.016) is yielded as a coarse crystalline product. In the solid K⁺ and HCN ions occur. As expected two significantly differing bond-distances C? N (117.3(5) pm) and HN? C (128.7(5) pm) have been found in the anion. According to IR-spectroscopy a non linear group N? C? N (174.4(4)°) is observed.     

Darstellung und Eigenschaften von 2-Alkyl- und 2-Allyl-acetoacetaniliden

The preparation of 2-alkyl and 2-allyl acetoacetarylamides is described. By interpretation of mass spectra a general fragmentation scheme of these compounds is proposed. NMR-spectroscopic investigations show, that alkylated acetoacetarylamides exist in the keto form only. Therefore they are unable to form metal-chelates.     

Uber die Darstellung und Eigenschaften von Hexathio- und Hexaselenohypodiphosphaten

Preparation and Properties of Hexathio- and Hexaselenohypodiphosphates The compounds mentioned in Tab. 1 have been synthesized by reaction of stoichiometric mixtures of the elements at elevated temperatures. Their properties were investigated. According to X-ray analyses, particulary of the compounds Fe₂P₂S₆ and Fe₂P₂Se₆ they belong to the hexachalcogenohypodiphosphates.