Marcel Graffeuil

An answer to the spiro versus ansa dilemma in cyclophosphazenes: Part I. N3P3Cl4[NH(CH2)3NH]

Abstract Structural investigation, mainly by mass spectrometry and X-ray crystallography, of the product obtained from the reaction of propylenediamine and N 3 P 3 Cl 6 shows it to have a monospiro structure. It is demonstrated that in this case data collected through indirect structural methods such as IR or NMR spectroscopy could not provide a priori the right answer.

Covalent binding of non-effective diaziridinocyclotriphosphazenes to natural polyamines as tumor finders makes potential anticancer agents

Covalent binding of diaziridinocyclotriphosphazenes, reputed as non-effective antitumor agents, to natural polyamines as tumor finders gives vectorized diaziridinocyclotriphosphazenes which display a significant effectiveness on murine tumors in vivo.

On the Scent of Dandelion Dendrimers. Part I. Cyclophosphazenic Hexapodanes as New Cores

Abstract Aminolysis of N3P3Cl6 by long-chain diamines, H2N—(CH2) n —NH2 (n  6), leads regiospecifically to hexadangling (or hexapodanes) monomeric species provided it was achieved on alumina impregnated with potassium hydroxide. These reactions run instantaneously at room temperature. Such hexapodanes constitute starting materials (cores) for future design of spherical (i.e. aesthetically similar to dry dandelion flowers) cyclophosphazenic dendrimers.

An answer to the spiro versus ansa dilemma in cyclophosphazenes: Part X. The serendipitous chemistry of the genuine cyclophosphazenic monoANSA derivative N3P3Cl4[HNCH2)2OCH2)2NH]

Abstract Aminolysis of the genuine monoANSA derivative, N 3 P 3 Cl 4 [HN(CH 2 ) 2 O(CH 2 ) 2 NH], leads to neat new B.A.S.I.C. structures in which the chlorine atoms trans to the ANSA arch are never involved. This is the first time to our knowledge that non-reactive chlorine atoms of a phosphonitrilic chloride trimer are made conspicuous.

Interprétation quantique des propriétés physicochimiques des alkylamines

Abstract A large set of physicochemical properties of alkylamines is investigated within the framework of the CNDO/2 approximation on the basis of a choice of a standard rigid geometrical model. The preferred theoretical conformations obtained in this way are identical to the experimental ones, when known. The trend of the barriers to rotation and inversion in methylamines is perfectly reproduced as well as the variation of dipole moments and ionization potentials. Finally, the degrees of acidity and basicity in the gas phase (as provided by ion cyclotron resonance) are also reproduced. It is clearly shown that, under such conditions, the CNDO/2 method should be used in concert with the classical physical methods by any chemist, even an experimentalist, who wishes to gain an understanding of the behaviour of electronically localized systems.

“DRY MEDIA PROCESS”: A CHEMAC (CHEMICAL MACHINERY) FOR THE AMINOLYSIS OF HEXACHLOROCYCLOTRIPHOSPHAZENE ON SOLID SUPPORTS

Abstract Aminolysis of N3P3CI6 by lipophilic long-chain monoamines runs regiospecifically when achieved on some suitable solid supports constituted from impregnated or not alumina and it allows the synthesis in a very neat way of some aminocyclophosphazenes of interest as precursors of new bio-materials.

The role of aziridinyl cyclophosphazenes and related compounds as anticancer agents. A tentative quantum mechanical approach

Abstract The electronic structures of the various conformations and allotropic species of two promising anticancer drugs, namely MYKO 63 and SOAz, have been calculated using the CNDO/2 approximation. The results allow prediction of the acidity (in the Lewis sense) of the aziridinyl-bearing atoms of the drugs which corresponds to the optimum anticancer activity possible upon coordination to DNA, as the Lewis-base target.

Une correlation entre les rendements radiochimiques en hydrogène et les énergies de liais ons calculées pour des familles d'alkènes, d'amines et d'alcools liquides

Abstract A quantum calculation of bond energies for some alkenes, amines and alcohols in the ground state allows the hydrogen yield obtained on irradiation of such molecules to be interpreted. This yield increases normally with the length of saturated chain for alkanes, alkenes and amines, in contrast with alcohols. The behaviour of alcohols could not be interpreted, even when hydrogen bonds, which characterize these alcohols in the liquid state, were included in quantum calculations.