Douraid Houalla

On the extension of the atherton-todd reaction to the 1-organyloxy 1-hydridobicyclophosphoranes

Abstract The 1-methoxy 1-hydridobicyclophosphorane 1 undergoes oxidation reaction with CCl 4 in basic solutions which allow the replacement of the hydrogen linked to phosphorus by several nucleophile groups. The same reaction carried out with the bicyclophosphorane 8 leads to a new compound 10 in which two P v atoms are included in a ten membered ring.

Phosphoranes bicycliques a liaison PH : Bases de Lewis potentielles

Abstract By reaction of Borane Dimethyl Sulfide on the bicyclophosphorane 1 the adduct 2 is obtained with 56 % yield; by-products 3 and 4 are characterized .

NEW MACROCYCLES CONTAINING BICYCLOPHOSPHORANE MOIETIES IV1. MACROCYCLES ISSUED FROM POLYETHYLENEGLYCOLS AND TRIETHANOLAMINE

Abstract New symmetric and mixed macrocycles containing bicyclophosphorane moieties 3, 4, 5, 6, 9 and IV have been obtained by a Todd reaction between the precursors 1, 2, and diethyleneglycol DEG, triethyleneglycol Tri.EG and tetraethyleneglycol Tet.EG. The reaction of the precursor 11 with triethanolamine Tri.EA afforded the first cryptand bearing pentacoordinated phosphorus atoms 12.

Bicyclophosphoranes Containing Macrocycles

Abstract Pentacovalent Phosphorus containing Macrocycles, 1,2,7 have been obtained by a general method applicable to all α-ω diols.

NOUVEAUX MACROCYCLES BICYCLOPHOSPHORANIQUES II MACROCYCLES MIXTES DÉRIVANT DE 3-OXO, 3-AMINO ET 3-THIO- 1,5-PENTANEDIOLS

Abstract De nouveaux macrocycles du phosphore pentacovalent comportant deux (1-5), trois (6,7) et quatre groupements bicyclophosphoraniques (8-10) ont ete obtenus par une reaction de Todd entre des bis-(hydridobicyclophosphoranes) et quatre 1,5-pentanediols H[sbnd]O (CH2)2[sbnd]Y[sbnd](CH2)2[sbnd]OH (Y = O, S, N-t.Bu, N-Ph). Mot-cles: Hydridobicyclophosphoranes; macrocycles du phosphore pentacovalent; reaction de Todd. New bis (1-5), tris (6,7) and tetrakis (bicyclophosphoranes) containing macrocycles (8-10) have been obtained by a Todd reaction between bis(hydridobicyclophosphoranes) and four 1,5-pentanediols HO[sbnd](CH2)2[sbnd]Y[sbnd](CH2)2[sbnd]OH (Y[dbnd]O, S, N-t.Bu, N-Ph).

Dioxazaphosphocanes à liaison P-H, nouveaux complexants du calcium associant les groupements phosphoryle et amide

Abstract The formation of calcium complexes with four 2-oxo σ 4 λ 5 dioxazaphosphocanes has been investigated by means of IR and 31 P NMR spectroscopy. The stoichiometry of these complexes shows that two heterocycles moieties containing each an amide and a phosphoryl group are needed to complex one Ca ++ ion

BICYCLOPHOSPHANES ET DIOXAZAPHOSPHOCANES : RÉACTIVITÉ ET DIFFÉRENCES CONFORMATIONNELLES

Abstract The stereochemistry as well as the molecular modelling of the dioxazaphosphocanes 3a - 3c, 4a - 4c, 9, 11, 12, 13 and 14 underline the direct connexion between the conformation of the dioxazaphosphocane eight membered ring and the substitution on the carbon atoms of this ring.

MUTAROTATION ARISING FROM STEREOLABILE PENTACOORDINATED PHOSPHORUS

Abstract The purpose of this paper is to show that optical rotation is a convenient method for studying the intramolecular stereolability in pentacoordinated species, particularly phosphorus derivatives. In chemistry, it is difficult to present a completely new idea and we will deal with this topic under several headings.

MOLECULAR STRUCTURES OF NOVEL MACROCYCLES CONTAINING BIS(BICY CLOPHOSPHORANES)

Abstract Single crystal X-ray diffraction studies of the macrocyclic bis(bicyclophosphoranes), [N(CH2)CMe2O)2PO2]2[(CH2)2S(CH2)2] (1) and [N-(CH2CMe2O)2PO2]2[(CH2)2 NPh(CH2)2][(CH2)2N-tBu(CH2)2] (2). revealed trigonal bipyramidal structures at the phosphorus atom. A comparison is made with the structures of related bicyclic phosphoranes containing similar ring systems that comprise both saturated (1–4) and unsaturated (5–8) members. A molecular mechanics treatment is performed which shows close agreement between the calculated and X-ray structures of 1 and 2.

Bicyclic phosphanes: synthesis, stereochemistry, and conformation

From the new family of 2,8-dioxa-5-aza-1-phosphaIIIbicyclo[3.3.0]octanes (bicyclic phosphanes)(1)–(5), three derivatives (3)–(5) were studied by synthesis, oligomerization, and n.m.r. spectroscopy. Conformational analysis shows that the five-membered rings take on an envelope conformation. The orientation of the folds is known for the majority of the compounds. Comparison of stereochemical data between phosphanes (2)–(4) and the corresponding 1-phenyl-2,8-dioxa-5-aza-1-phosphaVbicyclo[3.3.0]octanes (bicyclic phosphoranes)(7a)–(9a) underlines the conformational consequences due to the change of hybridization of the nitrogen and phosphorus atoms.