Quecksilber‐ und Silber‐Derivate von Diphenylphosphinyl‐ und Diäthylphosphono‐diazomethan

Abstract

Bequeme Synthesen fur Diphenylphosphinyl-bzw. Diathylphosphono-diazomethan (4a bzw. 4b) durch Amin-Diazotierung werden beschrieben. Beide Diazoverbindungen reagieren mit Quecksilber-bzw. Silberoxid zu den Metall-Derivaten 5a, b und 6a, b. Mercuric and Silver Derivatives from Diphenylphosphinyl-and Diethylphosphono-diazomethanel)Convenient syntheses for diphenylphosphinyl-and diethylphosphono-diazomethane (4a and 4b) by amine diazotization are described. Both diazo compounds react with mercoric and silver oxides to the metal derivatives 5a, b and 6a, b.Im Rahmen von Untersuchungen uber Phosphono-und Phosphinyl-diazoalkane 2 3 sowie Phosphono-und Phosphinyl-carbene 4) haben wir uns auch mit der Synthese metallierter PO-substituierter Diazoverbindungen befaRt. Der erste Vertreter dieser Stoffklasse war der von Buchner 5 ) aus Diazoessigsaure-athylester und Quecksilberoxid hergestellte Quecksilber-bis-[diazoessigsaure-athylester] ; ihm folgten erst in neuerer Zeit weitere Synthe~en6~7) sowie die Metallierung von a-Diazo-carbonyl-Verbindungen mit Silberoxid 8).Diphenylphosphinyl-und Diathylphosphono-diazomethan (4a und 4b), deren analoge Metall-Substitution die vorliegende Mitteilung behandelt, sind bereits be-1) XIII. Mitteilung uber Untersuchungen an Diazoverbindungen und Aziden; XII. Mitt. :

Methylation of Ylidene‐Triazenes: Insight and Guidance for 1,3‐Dipolar Cycloaddition Reactions

“…Although examples of the former have been reported, their Cu-catalyzed cycloaddition is currently limited to haloalkynes and proceeds by a mechanism that is still being established. Difunctionalized azides are also synthetically daunting targets, however a simpler analogue is an ylidene-triazene (Y), the coupling product of an Nheterocyclic carbene (NHC) to an azide, [28][29][30][31][32][33][34] which can be viewed as a zwitterion (Z) that is suitable to engage in dipolar cycloaddition reactions ( Figure 1). Figure 1.…”

λ5-Phosphorus-Containing α-Diazo Compounds: A Valuable Tool for Accessing Phosphorus-Functionalized Molecules

“…Although the diethyl analogue of 5a had been already prepared via a different route (see section ), this work represents the first example in which a dialkyl diazomethylphosphonate could be obtained in pure form by short-path distillation. Following this procedure, Regitz et al prepared diethyl α-diazomethylphosphonate ( 5c ), diphenyl α-diazomethylphosphinoxide ( 5d ), and methyl α-phenyl-α-diazomethylphosphinate ( 5e ) in 51%, 45%, and 16% yield, respectively. , This protocol was also applied by Marinozzi et al to the multigram scale synthesis of the diisopropyl analog 5b . Recently, some dialkyl aminomethylphosphonates became commercially available, thus simplifying this synthetic protocol.…”

Synthesis of Aminopyridazines from Aminocyclopropenylium Salts and Diazomethyl Compounds [1]

“…Prepared according to reported procedures: 12a [22], 12b (23J, 12c [241. 12d [25], 12e [22], l2f (26], 12g (27], 1211 (28], 12i [29J.…”