Über die SiN‐Bindung, XXVIII. Umsetzungen mit Azidosilanen

Abstract

4Durch Umsetzung von Butylaminosilanen rnit Benzazid, von Halogensilanen mit LiN3 oder Trimethyl-azidosilan, durch Komproportionierung von Diamino-und Diazidosilanen und durch Chlorierung von Hydrogen-azidosilanen wurden einige Azidosilane rnit zusatzlichen funktionellen Gruppen dargestellt. -Die thermische Zersetzung von Phenyl-diorganylazidosilanen fuhrt zu N.W-Diphenyl-tetraorganyl-cyclodisilazanen (1 -3). In Gegenwart von Benzophenon bilden sich beim thermischen Zerfall der gleichen Azidosilane N-silylierte Benzanilide (5, 6). --Die Addition von Azidosilanen an Nitrile liefert 2-Silyl-5-organyl-tetrazole (7-9), die heim Erhitzen unter N2-Abspaltung in 4-Disilylamino-3.5-diorganyl-l.2.4triazole (10, 11) iibergehen. In Gegenwart von Nitrilen zerfallen die Silyltetrazole unter Bildung von 2-Silyl-1.2.4-triazolen (12,13), rnit Siiurechloriden reagieren sie zu 2-Acyl-5-organyltetrazolen, die beim Erhitzen N2 abspalten und sich in 2.5-Diorganyl-1.3.4-oxadiazole (14, 15) umlagern. -Die Addition von Azidosilanen an Olefine ergibt N-Silyl-aziridine (16, 17). Aus Azidosilanen, tert.-Butylchlorid und SbClS schlieRlich bilden sich iiber Addukte 2-[Silyl-methyl-imoniol-propan-hexachloroantimonate (18), die bei der Hydrolyse in Disiloxane, Methylamin und Aceton zerfallen.

Synthesis and Functionalization of 5‐Substituted Tetrazoles

“…[83] This compound had convenient properties, such as stability, solubility in organic solvents, and a relatively high boiling point (95-96°C). [83] This compound had convenient properties, such as stability, solubility in organic solvents, and a relatively high boiling point (95-96°C).…”

Synthesis of New Tetrazole‐Substituted Pyroaminoadipic and Pipecolic Acid Derivatives

“…121Ϫ122°C (ref. [31] 125Ϫ126°C) 1 Synthesis of Dimethyl 2-Bromo-5-(5-substituted tetrazol-2-yl)hexanedioates 2 and Dimethyl 2,5-Bis(5-substituted tetrazol-2-yl)hexanedioates 2Ј: NEt 3 (15 mmol) was added dropwise to a solution of 5-substituted tetrazole (10 mmol) in 240 mL of anhydrous acetone. [12] The mixture was stirred at room temperature for 15 min, and dimethyl (R,S)-2,5-dibromohexanedioate (1.1 mol), dissolved in the minimum amount of acetone, was then added.…”

Azide Chemistry – An Inorganic Perspective, Part II[‡][3+2]‐Cycloaddition Reactions of Metal Azides and Related Systems

“…That frequently only mixtures of tetrazoles, 1,2,4-triazoles and 1,2,4,5-tetrazines (resp. 4-amino-1,2,4-triazoles) [323] are obtained by this method diminishes its value as a synthetic procedure, however (see below). [322] Only recently these difficulties have brilliantly been overcome by applying "click-type conditions" to these kinds of transformations, i.e., work with transition metal catalysts (Cu 2 O vs. nontoxic, environmentally friendly iron salts) in protic media (see also section 1.5.2).…”

“…[330] Still, silylated tetrazoles as such resulting from SiMe 3 (N 3 ) and nitriles are also of interest; their thermolysis like that of the organic 2,5-disubstituted counterparts to give nitrile imines proves their initial configuration and provides access to 2-trimethylsilyl-1,2,4-triazoles through trapping with, e.g., benzonitrile, or to 4-bis(trimethylsilyl)amino-1,2,4-triazoles through dimerization. [323,331,332] From a mechanistic point of view it is interesting that the reaction of trimethylsilyl azide with trichloroacetonitrile to give (explosive(!)) 1-silylated(?)…”