Y. Leroux

ETUDE STRUCTURALE DE L'ACIDE BUTANE HYDROXY-1 AMINO-4 DIPHOSPHONIQUE-1,1′

Abstract Structural study using X-Ray Crystallography of the amino hydroxy diphosphonic acid of the title has been done. The final objective is to use this functionalized hydroxy diphosphonic acid in complexation study and in organic synthesis of biological derivatives by the way of the amino group. Results are discussed on the basis of the environment of phosphorus atoms and on the molecular geometry around the central carbon atom.

Préparation et utilisation de lithiens de mono- et disilanes alléniques fonctionnels

Abstract Silylated propargylic ethers treated with butyllithium at −40°, constitute an important source of functional silylated allenes. A second metallation when it is possible, allows the synthesis of a great number of functional mono or polysilylated allenes. Reactions described present a great interest for the preparative point of view both by the variety of products and the speed and easiness of the synthesis.

Reactions de metallation dans la serie des spirophosphoranes a liaison PH. Formation de la liaison PVC

Abstract We report here the generation and reactions of reagents such as A, in which M = Li or Na. The action of various metallation reagents (RLi, R 2 NLi, HNa, NH 2 Na) in THF at room temperature has been tested on 2,2,3,3,7,7,8,8-octamethyl-1,4,6,9-tetraoxy-5-phospha(V)[4.4]spirononane. Only R 2 NLi and NH 2 Na are effective. The metallated intermediate is probably an oxanion rather than a phosphanion. Some coupling reactions of these reagents with various RX and their use in hydroxyspirophosphorane synthesis are described.

ETUDE STRUCTURALE DU COMPLEXE DE l′ACIDE ETHANE HYDROXY-1 DIPHOSPHONIQUE-1,1′ AVEC LE CUIVRE II

Abstract Structural study using X-ray cristallography of the complex of the title has been done. Our aim in that study is to be able afterwards to compare it with other cupric complexes dealing with functionalized hydroxy diphosphonic acid and to use these results in the way of organic synthesis. Results are discussed on the basis of the environment of phosphorus atoms and on the molecular geometry around the central carbon atom.

Supramolecular assembly of substituted hydroxy-bisphosphonates with cupric ion. Influence of the chain functionalization

Abstract As part of a general study of hydroxy-bisphosphonic acids (HEBP), R-C(OH)(PO3H)2, three Cu (II) complexes with R˭CH3; R˭-(CH2)3-NH2 and R˭-(CH2)5-NH2, were prepared and analysed by X-Ray diffraction methods. The substitution of the methyl group in HEBP (3) by an aminopropyl (1) or by an aminopentyl (2) chain led to a drastic modification of the ionic self-assembly in the crystal and completely different polyhedral complexation networks around the Cu (II). A polymeric chain formation is observed in (3), whereas (1) and (2) display discrete tetrameric and dimeric arrangements. The results are discussed on the basis of the environment of the phosphorus atoms and the molecular geometry around the central carbon atom of the hydroxy-bisphosphonic moiety. These results are further compared to their ability for ionic transport and/or extraction.

ÉTUDE DE LA COMPLEXATION DU CADMIUM ET DU ZINC AVEC L'ALENDRONATE (ACIDE 4-AMINO-1-HYDROXYBUTYLIDÈNE-1′1-BISPHOSPHONIQUE)

Abstract Structural study using X-ray cristallography of the complexes of the title has been done. Alendronate is already known to be a very good chelator of divalent cations and supramolecular species obtained with alendronate and these cations are very stable and make them able to be used in biological systems. Our study points out that the size of the cation strongly modifies the structure of the complex. With Cu(II) and Zn(II) which are two cations with proximate ionic radii one cation is put in the centre of the coordination system and structures are isomorphous. On the other hand, with Cd(II), a binuclear complex is obtained. Results are discussed on the basis of these structures.

SYNTHÈSE D'α CÉTOPHOSPHONATES ET D'ESTERS D'HYDROXY MÉTHYLÈNE DIPHOSPHONATES III

Abstract The phenylacetic chloride reacts with the trimethyl phosphite and the methoxy tetramethyl dioxaphospholane to give hydroxyvinyl phosphonates 1 and 6 which are starting products in the synthesis of diphosphonates 11 and 16. The reactions of crotonyl chloride a, trans cinnamoyl chloride b, methacryloyl c and dimethyl acryloylchloride d with the same phosphites are also studied. Stable spirophosphoranes 26′, 29 and 25′ are obtained from methoxy tetramethyl dioxaphospholane and a, b, c respectively; d leads quantitatively to the formation of a stable keto phosphonate 27.

Reactions des cetones acetyleniques avec les phosphites et les aminophosphites en presence de reactifs de piegeage protiques. Synthese, mecanisme de fo

Abstract Cyclic and acyclic trivalent phosphorus compounds ( 1 , 2 , 3 , 4 ) were reacted with activated carbonyl acetylenic compounds as 1-4-diphenyl-2 butyne-1,4-dione ; 1-Methoxy-phenyl-4-Phenyl-2-Butyne-1,4-dione ; 4-oxo-4-phenyl-Methyl-2-butynoate and 1,3-diphenyl-1-propyne-2-one. All these reactions were performed in presence of protic trapping reagents ZH such as methanol a , phenol b or phtalimid c . All these reactions lead to a very unstable 1,3 dipolar species like P+-C(R)C-C(O)-R which is not detected even at low temperature. This species is protonated instantaneously with the protic trapping reagent ZH giving the following intermediate P+-C(R)CH-C(O)R,Z-]. Further, Z- may attack the phosphorus atom with formation of a vinylic phosphorane : compounds series A and C, or Z- may attack the electrophilic center of the keto group leading either to ylid formation i.e. compounds serie B or to spirophosphoranes formation i.e. compounds serie D. Mechanisms involved in these reactions are studied.

ETUDE STRUCTURALE DU TÉTRAESTER MÉTHYLIQUE DE L'ACIDE ETHANE HYDROXY-1 DIPHOSPHONIQUE-1,1′ ET DU TETRAESTER MÉTHYLIQUE DE L'ACIDE MÉTHANE HYDROXY-1 PHÉNYL-1 DIPHOSPHONIQUE-1,1′

Abstract Structural study using X-Ray crystallography of the two symmetrical diesters 1 and 2 of the titles has been done. Results are discussed on the basis of the environment of phosphorus atoms and on the molecular geometry around the central carbon atom.

Reactions des composes du phosphore tricoordine avec les cetones et les esters ethyleniques : Prototropie, cyclisation, expansion de cycle

Resume Addition of trivalent phosphorus compounds with α,β-ethylenic ketones and esters leads to examples of prototropy or cyclisation or rearrangement with ring expansion from 5 to 7 atoms.