73000-88-1

Upstream product

• 463-51-4 Ketene 
• 57694-92-5 N-Methyl-N-(triphenylsilylethinyl)anilin 
• 67370-99-4 N-Methyl-N-(trimethylstannylethinyl)anilin 
• 58528-69-1 Methyl-phenyl-[(triphenylstannanyl)-ethynyl]-amine 

Relevant academic research and scientific papers

(Aminoethinyl)metallierungen, VIII. Umsetzungen von β-silylierten Inaminen mit Keten; Konkurrenz von (Aminoethinyl)silylierung und -Cycloaddition

(Silylethynyl)amines 1 react with ketene (2) to yield according to the principle of the -cycloaddition preferentially the 2-silyl-2,3-butadienamides 6 and the 3-amino-2-silyl-2-cyclobuten-1-ones 7.The latter ones hydrolyze easily to the corresponding silyl-free cyclobutenones 8.In some cases one can isolate besides these compounds (see the reactions of 1a and 1e) or exclusively (see the reaction of 1d) 1:2- and 1:3-adducts, the formation of which can be explained via the non detectable (3-siloxy-3-buten-1-ynyl)amines 4 .These enyn-amines add to their C/C triple bond a second molecule of ketene (2) to give the allene carboxamides (see 5d) and cyclobutenones 9.The compounds 9 easily hydrolyze to the corresponding acetylcyclobutenones 10 and they react with exceeding ketene (2) to form the 1:3-adducts 11.The cyclobutenone 9d isolable in substance adds diphenyl ketene and tert-butylcyanoketene in the same way to give the analogous chain prolongation products 14 and 15.

(AMINOETHINYL)METALLIERUNGEN. VII. SYNTHESE UND REAKTIVITAET VON (3-STANNYLOXY-3-ALKEN-1-INYL)AMINEN

The C=O double bond of diphenylketene inserts into the tin-acetylenic carbon single bond of β-stannylated ynamines.The formation of 4,4-diphenyl-3-stannyloxy-3-buten-1-ynyl amines is proved partly by spectroscopic data, partly by isolation.Under detachment of the stannyl group they hydrolyze relatively easily to the corresponding acyl ynamines and react with acyl chlorides to give the corresponding 3-acyloxyenynamines.N-Methyl-N-(4,4-diphenyl-3-triphenyl-stannyloxy-3-buten-1-ynyl)aniline yields under the conditions of chromatography on silica gel a destannylated β-naphthol derivative; the same enynamine isomerizes in CDCl3 solution spontaneously to 4-(N-methylanilino)-1-phenyl-3-triphenylstannyl-2-naphthol, the structure of which is established by an X-ray analysis.The reaction of the β-stannylated ynamines with ketene or dimethyl-ketene directly gives the corresponding acyl ynamines, which are characterized by the reaction with tosylazide as crystalline diazo compounds.By addition of an excess of ketene the 2-acetyl-3-amino-2-cyclobuten-1-ones are formed as 1:2 adducts.