Reaction des lithiens avec les organophosphores. Reaction d'addition du t-butyllithium sur le noyau benzenique des sels de phenylphosphoniums

A new reaction of organolithium compounds with phosphonium salts is described; reaction of t-butyllithium with dibenzylaminophosphonium or tetraphenylphosphonium bromides takes place through addition of the t-butyl group on a benzene ring at the position para to the phosphorus atom, the ylid formed reacts in a characteristic Wittig reaction with p-tolylaldehyde.     

Pd/C-catalyzed room-temperature hydrodehalogenation of aryl halides with hydrazine hydrochloride

Treatment of aryl and heteroaryl halides with catalytic amounts of Pd/C in the presence of hydrazine hydrochloride in basic medium (sodium hydroxide or sodium t-butylate) at room temperature leads to the corresponding hydrodehalogenation products with high selectivity. Aryl iodides, bromides, chlorides and fluorides can be reduced using this reagent combination. The reduction is compatible with various electron-donating or electron-withdrawing groups.     

Synthetic Applications of Phosphonium Diylides

Abstract

Phosphonium diylides 1 react with electrophiles leading to new monoylides which permit., by a Wittig reaction, the E stereoselective synthesis of various di- or tri-substituted α,β-unsaturated functionalized compounds.     

Polarographic Investigations of Functionalized Alkanephosphonic Acids. Part II

Abstract

In this presentation we attempted to verify the enigmatical problem of the polaro-graphical activity of the phosphonic function, especially its electrochemical reduction. Thus, the first report on the polarographic activity of the nitro substituted phenylphos-phonic acid was presented by Kosolapov and Jenkins in 1957 [2].     

New Cyclotriphosphazenes with P-CAr Bonds

Abstract

We describe some new cyclotriphosphazenes in which the phosphorus substituents are either free rotating aromatic or heteroaromatic groups, or rigid spirobiaryl units.     

New Applications of the Lithiated Phosphinimine Ph3P=N-Li: Synthesis of α,β-Unsaturated Nitriles and P=N-P Linked Phosphinimines

Abstract

The reaction of Ph₃P-N-Li⁽¹²⁾ with various α,β-unsaturated esters gives access to new N-(α,β-unsaturated acyl) phosphinimines. which can undergo intramolecular aza-Wittig reaction (at 65 - 110°C) to afford the corresponding nitriles.     

Sodium and Onium Persorate Salts as Decontaminants of Neutotoxic Organophosphorus Compounds

Abstract

We compare the Sodium Perborate and various Phosphonium and Ammonium Perborates in their abilities to hydrolyse a series of phosphoric and phosphonic acid esters [OP].     

Destruction of Toxic Organophosphorus Esters by Oxidative α-Nucleophilic Reagent

Abstract

Despite its self-decomposition, Magnesium MonoPeroxyPhtalate 4 is an excellent reagent to totally detoxify phosphonothiolate 1 and fluoridate 2 in basic aqueous medium.     

New Applications of Ph 3 P=N--Li in Organic Synthesis and Heteroatom Chemistry

The lithium triphenylaminophosphonium azayldiide 1 proved again to be a very good tool in organic synthesis, allowing further synthesis of various compounds such as vinyl nitriles, aromatic or heteroaromatic nitriles, and mono-, bis-, and trisphosphinimines.