J. Barrans

Formation of stable cyclic dicoordinated phosphorus compounds by reaction of cyclophosphazanes with lewis acids

Abstract Thermal equilibrium between dicoordinated and tricoordinated phosphorus compounds (i.e. benzodiazaphosphole ⇄cyclotetraphosphazane) has been observed. The dicoordinated compounds have been stabilized by complexing with Lewis acid and isolated.

Action des composes dicarbonyles-1,2 sur des composes du phosphore dicoordonne a liaison pn et sur leurs oligomeres.

Abstract Triazaphospholes react with 1,2-diketones to give spirocyclic phosphorus compounds by a 1.1 addition at phosphorus atom; with o-quinones one obtains spirobicyclic hexacoordinated phosphorus compounds. The reaction of 1,2-diketones with λ 3 -phosphazene oligomers appears different, to some extent, and can be used as a test for the existence of a monomer-oligomer equilibrium.

Composes du phosphore dicoordonne: Reaction de diaza-1,4 dienes-1,3 disubstitues sur les derives de diazaphosphole. Du triazaphosphole-1,2,4,3 et de precurseurs de composes du phosphore dicoordonne

Addition of diazadienes 5 to dicoordinated phosphorus derivatives such as triazaphospholes 1 or diazaphospholes 3 leads to new tetracoordinated phosphorus spirocompounds 2 or 4. The tricoordinated phosphorus species 7 and 9 exist in a monomer tetramer PIII equilibrium but only the monomeric PII form reacts with diazadienes 5 leading to the spirocompounds 8 and 10. The monomers of 7 and 9 stabilized by complexation react with 5 to afford spirocompounds analogous to 2 and 4. In all these reactions the dicoordinated phosphorus atom is a good electrophile.

Composes du phosphore diccordonne: Synthese et reaction de phosphazenes acycliques

Abstract The reaction of Mes-PCl 2 with several amines gives new compounds, oligomers of Mes-P=N-R. Chemical properties of these oligomers are investigated: action of alcohols and disubstituted amines (XH) gives , the formation of which are only consistent with the presence of a dicoordinated phosphorus compound, Mes-P=N-R, in equilibrium with a tetramer

Spirophosphazenes and the parent triazaphosphole : differences and similarity in chemical reactivity

Abstract The first step of hydrolysis of compounds 1 , 2 and 4 involves the protonation of the PN nitrogen atom. 3 does not react with water in the absence of a catalyst. Protonation of compounds 1 – 3 by a strong acid such as CF3SO3H is studied by 15N and 31P nmr spectroscopy. In all cases the PN nitrogen appears to be the strongest basic site.

Composes du phosphore dicoordonne. Les bitriazaphospholes-1,2,4,3: Synthese et proprietes

Resume The title compounds were obtained by reaction of diamidrazones with tris(dimethylamino)phosphine. The bitriazaphosphole structure is consistent with mass spectra. The reactivity of these new compounds and of triazaphosphole derivatives seems to be the same.

Synthesis of the first examples of 1H- and 4H-1,2,4,3λ3-triazaphospholes via unexpected ring-contraction reactions

The reaction of the Schiff bases of benzamidrazone or diaminomaleonitrile with bis(dimethylamino)chlorophosphine or tris(dimethylamino)phosphine affords new 1H, 2H-, or 4H-1,2,4,3λ3-triazaphospholes or 1,3,2λ3-diazaphospholes with the formation of triaza- or diaza-phosphorines as intermediates.

Thermal Behaviour of Some Organ0 Phosphorus Compounds

Abstract So far organophosphorus chemists have been interested in synthesizing low coordinated phosphorus compounds and in studying them in solution at temperatures rarely above 300 °C. As a matter of fact there are few reports on the behaviour of dicoordinated phosphorus molecules at temperatures above 500 °C under low pressure. Another interesting point is that such a study would allow to assess the correla- tion between mass spectral processes and thermal ones.

Phosphorus derivatives of amide oximes. Part 1. Synthesis of N2-[bis(dimethylamino)phosphinoyl]amidines, 4,6-disubstituted 2,5-dihydro-1,3,5,2-triazaphosphorine 2-oxides, and 3-dialkylamino-1-dimethylamino-1H-2,1-benzazaphosphole 2-oxides

The reactions of tris(dimethylamino)phosphine with amide oximes gave three types of compound, depending on the amide oxime substituents and the temperature: N2-[bis(dimethylamino)phosphinoyl]amidines (1), 4,6-disubstituted 2,5-dihydro-1,3,5,2-triazaphosphorine 2-oxides (2), and 3-dialkylamino-1-dimethylamino-1H-2,1-benzazaphosphole 2-oxides (3). With unsubstituted amide oximes only compounds (1) were formed at room temperature; at 80 °C a 1 : 1 mixture of (1) and (2) was obtained. Compounds (3) were obtained only with N-alkylbenzamide oximes. The formation of compounds (1)–(3) can be explained in terms of an unstable CN–O–PIII intermediate. 31P CIDNP effects were observed during the formation of compounds (3), in support of a radical mechanism. 1H N.m.r. and i.r. data are discussed.

SYNTHESE DE NOUVEAUX DERIVES ORGANOPHOSPHORES BICYCLIQUES FONCTIONNELS

Abstract Cycloaddition of dichlorophenylphosphine with 3,4-bis(methylene)-thiolane affords a bicyclic phospholenium salt; further reactions with water and dihydrogen sulfide give new series of bicyclic phospholenes.