Reaction Of Ynamines Research Articles

The reaction of isoquinolinium N-phenylimide with 1-(diethylamino)propyne and carbon disulfide

The cycloadduct 1 exists in a mobile equilibrium with isoquinolinium N-phenylimide ( 2) and CS 2. The reaction of 1 with 1-(diethylamino)propyne ( 3) afforded the 1:1:1 products 4 and 5, the latter predominating with higher CS 2 concentration. The NMR spectra and an X-ray analysis of 4 clarified the structures. The hindered rotation about the CN bond of the N, N-diethylthiocarboxamide groups is responsible for the temperature-dependent dynamic processes observed in the 1H NMR spectra of 4 and 5. In analogy with the known reaction of the ynamine 3 with CO 2, the thiocarbamoyl-thioketene 11 is assumed as key intermediate which accepts the 1,3-dipole either at the CC or the CS bond. The reaction of ynamine 3 with CS 2 in the absence of 2 provided a 2:2 product in modest yield.

ChemInform Abstract: α‐Sulfinylamidines by the Reaction of Ynamines with N‐(Sulfinyl)arenesulfonamides.

Abstract22 α‐sulfinylamidines such as (IV) or (VI) are prepared by the title reaction via intermediates of type (III); from the ynamine (IX), both the E isomer (VIII) and the Z isomer (X) can be obtained.

ChemInform Abstract: Reaction of Ynamines with Aromatic Bifunctional Reagents.

AbstractThe reactions of the enynamines (I) with pyrocatechol (II), o‐aminophenol (IV) or o‐phenylenediamine (VI) proceed regiospecifically at the acetylenic bond to give the heterocycles (III), (V) and (VII).

Heterosubstituted acetylenes XXVII: Synthesis of 4-amino-2-pyridones by the reaction of ynamines with styrylisocyanates

Styrylisocyanates add to ynamines to give 4-amino-2 (1H) pyridones (III) by a 1,4-cycloaddition. Under the reaction conditions the 1:-adducts (III) are further N-acylated with a second mole of syrylisocyamate to urea derivatives (IV). These decompose upon heating into the parent compounds. N-, and O-methylation of III as well as IR, UV and NMR spectra confirm the proposed structures of the 1:1-and 1:2-adducts III and IV.

Les α-chloro-énamines—I : Acylation des Ynamines

Acid chlorides, phosgene, thiophosgene, thionyl chloride and aromatic sulfonyl chlorides readily add to ynamines to give α-chloro-enamines. The α-chloro-β-chlorocarbonyl-enamines (V) are thermally remarkably stable as illustrated by their distillation in vacuum without decomposition. The reaction of ynamines with oxalyl chloride led to 5-disubsituted amino-2,2-dichloro-3 (2H)-furanones (XIX) The structure of these α-chloro-enamines was established by hydrolysis, alcoholysis and aminolysis.