Über die gemeinsame Einwirkung von Ammoniak (Aminen, Iminen) und Tetrachlorkohlenstoff auf Phosphine, I

Abstract

rnEine neue Methode zur bequemen Darstellung von Amino(11nino)-phosplioniumchloriden wird beschrieben. Sie beruht auf der gemeinsamen Einwirkung von Ammoniak (Aminen, Tminen) und Tetrachlorkohlenstoff auf Phosphine. Neben dem Amino(1mino)-phosphoniumchlorid entsteht als einziges Nebenprodukt noch Chloroform. Der Reaktionsmechanismus wird diskutiert. The Simultaneous Action of Ammonia (Amines, Imines) together with Carbontetrachloride on Phosphines, IA new method for a convenient preparation of amino(imino)-phosphonium chlorides is presented. It involves the simultaneous reaction of ammonia (amines, imines) and carbontetrachloride with phosphines. Chloroform is the only by-product formed in the reaction. The possible reaction mechanism is discussed.Kiirzlich wurde berichtet, da13 Hexitphosphonite in Dioxan mit Tetrachlorkohlenstoff und Diathylamin glatt unter Bildung von Hexit-diathylamido-phosphonat reagieren 1). Diese Beobachtung veranlaBt uns, eigene Ergebnisse aus noch laufenden Untersuchungen iiber das Dreikomponenten-System Phosphin/Tetrachlorkohlenstoff 1 Amin mitzuteilen.In Weiterfiihrung unserer Versuche, S.S-Dimethyl-sulfoximin (1 a) und S.SDimethyl-sulfodiimin (1 b) an den Stickstoffatomen mit Phosphinen zu cyclischen und kettenformigen gemischten Sulfazan-Phosphazan-Verbindungenz.3) umzusetzen, fanden wir, da13 Athylen-bis(dipheny1phosphin) mit 1 a und 1 b in Gegenwart von CC4 nach GI. (1) reagiert :

Fused pyridines by a tandem aza‐wittig / heterocyclization strategy: Synthesis of 1,2,4‐triazolo[1,5‐a]pyridines and pyrido[1,2‐b][1,2,4]triazines

“…the modified Kirsanov reaction) [33] (Scheme 1). It is plausible that the amino group in the 6-position is more reactive than that attached to the ring nitrogen in the 1-position.…”

Fused pyridines by a tandem aza‐wittig / heterocyclization strategy: Synthesis of 1,2,4‐triazolo[1,5‐a]pyridines and pyrido[1,2‐b][1,2,4]triazines

“…the modified Kirsanov reaction) [33] (Scheme 1). It is plausible that the amino group in the 6-position is more reactive than that attached to the ring nitrogen in the 1-position.…”

High Spin Cobalt Complexes Supported by a Trigonal Tris(Phosphinimide) Ligand

“…Using a similar backbone, tris-alkoxide, -siloxide, and -carboxylate variants have been described, − and tris-phosphine precursors (Int1) bearing phenyl- or adamantyl substituents are readily prepared (Supporting Information). , However, attempts to convert Int1 to H 3 R L via traditional routes, including the usage of Me 3 SiN 3 6 or aminolysis of R 3 PCl 2 derivatives, proved unsuccessful; even after prolonged heating, incomplete conversion of Ph Int1 was observed upon exposure to excess Me 3 SiN 3 as monitored by 31 P NMR spectroscopy (Figure S18). We hypothesize that steric effects preclude incorporation of three bulky Me 3 SiN groups onto this constrained framework.…”

High Spin Cobalt Complexes Supported by a Trigonal Tris(Phosphinimide) Ligand

“…Using a similar backbone, tris-alkoxide, -siloxide, and -carboxylate variants have been described, [27][28][29] and tris-phosphine precursors (Int1) bearing phenyl-or adamantyl substituents are readily prepared (Supporting Information). [30][31] However, attempts to convert Int1 to H3 R L via traditional routes, including the usage of Me3SiN3 6 or aminolysis of R3PCl2 derivatives 32 proved unsuccessful; even after prolonged heating, incomplete conversion of Ph Int1 was observed upon exposure to excess Me3SiN3 as monitored by 31 P NMR spectroscopy (Fig S18). We hypothesize that steric effects preclude incorporation of three bulky Me3SiN groups onto this constrained framework.…”

Fused pyridines by a tandem aza‐wittig / heterocyclization strategy: Synthesis of 1,2,4‐triazolo[1,5‐a]pyridines and pyrido[1,2‐b][1,2,4]triazines

“…the modified Kirsanov reaction) [33] (Scheme 1). It is plausible that the amino group in the 6-position is more reactive than that attached to the ring nitrogen in the 1-position.…”

High Spin Cobalt Complexes Supported by a Trigonal Tris(Phosphinimide) Ligand

“…Using a similar backbone, tris-alkoxide, -siloxide, and -carboxylate variants have been described, − and tris-phosphine precursors (Int1) bearing phenyl- or adamantyl substituents are readily prepared (Supporting Information). , However, attempts to convert Int1 to H 3 R L via traditional routes, including the usage of Me 3 SiN 3 6 or aminolysis of R 3 PCl 2 derivatives, proved unsuccessful; even after prolonged heating, incomplete conversion of Ph Int1 was observed upon exposure to excess Me 3 SiN 3 as monitored by 31 P NMR spectroscopy (Figure S18). We hypothesize that steric effects preclude incorporation of three bulky Me 3 SiN groups onto this constrained framework.…”

High Spin Cobalt Complexes Supported by a Trigonal Tris(Phosphinimide) Ligand

“…Using a similar backbone, tris-alkoxide, -siloxide, and -carboxylate variants have been described, [27][28][29] and tris-phosphine precursors (Int1) bearing phenyl-or adamantyl substituents are readily prepared (Supporting Information). [30][31] However, attempts to convert Int1 to H3 R L via traditional routes, including the usage of Me3SiN3 6 or aminolysis of R3PCl2 derivatives 32 proved unsuccessful; even after prolonged heating, incomplete conversion of Ph Int1 was observed upon exposure to excess Me3SiN3 as monitored by 31 P NMR spectroscopy (Fig S18). We hypothesize that steric effects preclude incorporation of three bulky Me3SiN groups onto this constrained framework.…”

Fused pyridines by a tandem aza‐wittig / heterocyclization strategy: Synthesis of 1,2,4‐triazolo[1,5‐a]pyridines and pyrido[1,2‐b][1,2,4]triazines

“…the modified Kirsanov reaction) [33] (Scheme 1). It is plausible that the amino group in the 6-position is more reactive than that attached to the ring nitrogen in the 1-position.…”

High Spin Cobalt Complexes Supported by a Trigonal Tris(Phosphinimide) Ligand

“…Using a similar backbone, tris-alkoxide, -siloxide, and -carboxylate variants have been described, − and tris-phosphine precursors (Int1) bearing phenyl- or adamantyl substituents are readily prepared (Supporting Information). , However, attempts to convert Int1 to H 3 R L via traditional routes, including the usage of Me 3 SiN 3 6 or aminolysis of R 3 PCl 2 derivatives, proved unsuccessful; even after prolonged heating, incomplete conversion of Ph Int1 was observed upon exposure to excess Me 3 SiN 3 as monitored by 31 P NMR spectroscopy (Figure S18). We hypothesize that steric effects preclude incorporation of three bulky Me 3 SiN groups onto this constrained framework.…”

High Spin Cobalt Complexes Supported by a Trigonal Tris(Phosphinimide) Ligand

“…Using a similar backbone, tris-alkoxide, -siloxide, and -carboxylate variants have been described, [27][28][29] and tris-phosphine precursors (Int1) bearing phenyl-or adamantyl substituents are readily prepared (Supporting Information). [30][31] However, attempts to convert Int1 to H3 R L via traditional routes, including the usage of Me3SiN3 6 or aminolysis of R3PCl2 derivatives 32 proved unsuccessful; even after prolonged heating, incomplete conversion of Ph Int1 was observed upon exposure to excess Me3SiN3 as monitored by 31 P NMR spectroscopy (Fig S18). We hypothesize that steric effects preclude incorporation of three bulky Me3SiN groups onto this constrained framework.…”