Jürgen Bödeker

Cycloadditionen n-pyridyl(2)-substituierter azomethine mit heterokumulenen

Zusammenfassung N-Pyridyl(2)-substituted azomethines react with phenylisocyanate, diphenylketene and diphenylcarbodiimide to 2+2- or 4+2-cycloadducts. The structures of cycloadducts are confirmed by IR-, NMR- and mass spectra; the routes of their formation are discussed.

Nucleophile Reaktivität n-α-Heteroaromatisch substituierter thiophosphinsÄureamide

Abstract N -α-Heteroaromatic substituted thiophosphinic amides are alkylated by methyl iodide at the sulfur atom. The compounds predominantly exist as imidothiophosphinic acid- S -methylester-salts. N -2-Pyridylimidodiphenylthiophosphinic acid- S -methylester-hydroiodide with methyl iodide and benzene forms adducts and can be deprotonated to the free imidoester, which on heating isomerizes into an endocyclic N -methylated compound. Both the imidoester and the Na-salt of the diphenylthiophosphinic- N -2-pyridyl amide are transformed into the same S,N -dimethylated cation by methyl iodide. ab] N -α-Heteroaromatisch substituierte Thiophosphinsaureamide werden von Methyljodid am Schwefelatom alkyliert. Die Verbindungen liegen hauptsachlich als Imidothiophosphinsaure- S -methylester-Salze vor. N -Pyridyl(2)-imidodiphenylthiophosphinsaure-S-methylester-hydrojodid bildet mit Methyljodid und Benzol Addukte und lasst sich zum freien Imidoester deprotonieren. Dieser isomerisiert beim Erhitzen zur endocyclischen N -methylierten Verbindung. Sowohl der Imidoester als auch das Na-Salz des Diphenylthiophosphinsaure- N -pyridyl(2)amids geben mit Methyljodid das gleiche S,N -dimethylierte Kation.

Zur Lage der P=S-Valenzschwingung und zum Alkylierungsverhalten von Thiophosphinsäureamiden

Abstract The range of the ν(P=S)-absorption of thiophosphinic amides has been determined by an IR spectroscopic investigation of 30 derivatives. The band position of alkylated compounds can be used as a criterion for discerning between S- and N-alkylation. Diphenyl- and dimethylthiophosphinic amide react with methyl iodide to give isolable S-methylphosphonium sals. On the other hand the anion of dimethylthiophosphonic anilide is alkylated at the nitrogen atom of the ambivalent system.