Über Alkin‐amine, VIII Ω‐Diäthylamino‐phenylacetylen

Abstract

Die Umsetzung von Phenylacetylenlithium mit N-Chlor-diathylamin fiihrt neben dem Austausch Halogen/Metall und der Bildung von Diphenyldiacetylen zumw-Diathylamino-phenylacetylen (I), das auch aus Phenylacetylenmagnesiumbrornid und Chlordiathylamin hergestellt wird. Die Konstitution von I wird durch IR-Spektrum, Hydrdtisierung, Hydrierung und Addition von Diathylamin zu w.w-Bis-diathylamino-styrol bewiesen.Verbindungen der Acetylenylgruppe mit Nichtmetallen, wie Silicium, Sauerstoff und neuerdings Schwefel, sind gut bekannt. Trotz mehrfacher Versuche ist aber die direkte Verkniipfung von Stickstoffatomen mit der C E C-Bindung bisher nicht uberzeugend gelungen.

Synergic nucleophilic and electrophilic properties of carbenes. Synthesis of carbazoles, azafluorenes, .delta.-carbolines, and pyrido- and pyrimido[2,1-a]isoindoles by carbene rearrangement. Tracer studies of the mechanisms and an analysis of the carbon-13 NMR spectra of azafluorenes

“…The predominant regioselectivities of ring expansion in the diarylcarbenes studied here are shown (21a,i, 28,32,34). From these selectivities, it is evident that the carbene ring expansion cannot be regarded as an electrophilic substitution or addition, as it is well known that benzene is much more prone to electrophilic substitution than pyridine.…”

“…F. Analysis of the 13C NMR Spectra of Azafiuorenes. A detailed analysis of the l3C NMR spectra of 1-and 3-azafluorene was essential in order to elucidate the reaction pathways of phényl-3-pyridylcarbene (28). In particular, it was of paramount importance to distinguish carbon atoms 4a and 4b (for numbering, see Figure 2).…”

Synthesis of amines by the electrophilic amination of organomagnesium, -zinc, -copper, and -lithium reagents

“…21 If it is reacted with monochlorodiethylamine (ClN(C 2 H 5 ) 2 ) lithium phenylacetylide affords the corresponding tertiary amine in only 3% yield. 25 Methoxyamine 15 has been widely used for the amination of organolithium reagents.…”

Novel ynamide structural analogues and their synthetic transformations

“…Ynamides 1 (Scheme 1), the electron-deficient alternatives of the important but labile ynamines, [1][2][3][4][5][6][7][8][9][10][11][12][13][14] represent one of the most significant and versatile N-containing building blocks in organic synthesis. [15][16][17] Particularly, in the past 15 years, interests in this versatile building block have raised dramatically.…”