A Synthetic Study of Chiral α‐Hydroxy‐H‐Phosphinates Based on Proline Catalysis

A highly enantioselective synthesis of α‐hydroxyphosphinates was achieved based on the L ‐proline‐catalyzed aldol reaction of α‐acylphosphinates and acetone. Due to the preexisting chirality at the phosphorus center, mixtures of two diastereomers of the α‐hydroxyphosphinates were obtained in moderate to good yields, with simultaneously high enantioselectivity for both diastereomers. The products could be converted into α‐hydroxy‐H‐phosphinates with satisfactory yields. Furthermore, an unprecedented oxidation–reduction reaction of the α‐hydroxyphosphinates or α‐hydroxy‐H‐phosphinates to form phosphonates was observed, and the mechanism involved in such a chemical transformation is discussed.     

Novel Synthesis of Phosphinates by the Microwave-Assisted Esterification of Phosphinic Acids

1-Hydroxy-3-phospholene oxides (1 and 3) and phenyl-H-phosphinic acid (6) are converted to the corresponding phosphinic esters (2, 4, and 7, respectively) by reaction with simple alcohols on microwave irradiation. Under traditional heating conditions, the esterification does not take place, as in the cases of 1 and 3, or is highly incomplete, as in the case of 6. Steric hindrance in diphenylphosphinic acid prevents efficient microwave-assisted esterification.     

Efficient Asymmetric Hydrogenation of α‐Acetamidocinnamates through a Simple,Readily Available Monodentate Chiral H‐Phosphinate

An air‐stable, simple (R_P)‐mentylbenzylphosphinate, readily available in large quantities, can efficiently induce the rhodium‐catalyzed asymmetric hydrogenation of α‐acetamidocinnamates with high enantioselectivity (up to 99.6 % ee). Intramolecular hydrogen bonding plays an important role in this asymmetric induction.     

Hierarchical Helicates Bearing Phosphorus-Based Substituents in the Periphery

Phosphinate and phosphane substituted hierarchical helicates have been prepared, and the phosphinate derivatives could be characterized in the crystal. The helicate with phosphane substituents was submitted to an orientating study on catalysis, showing its potential to act as chelating ligand for the generation of active rhodium-based hydrogenation catalysts.     

New rac‐XP(O)(OC6H5)(NHC6H4‐p‐CH3) [X = N(CH3)(cyclo‐C6H11) and NH(C3H5)] and rac‐(C6H5CH2NH)P(O)(OC6H5)(NH‐cyclo‐C6H11) mixed‐amide phosphinates

The mixed‐amide phosphinates, rac‐phenyl (N‐methylcyclohexylamido)(p‐tolylamido)phosphinate, C₂₀H₂₇N₂O₂P, (I), and rac‐phenyl (allylamido)(p‐tolylamido)phosphinate, C₁₆H₁₉N₂O₂P, (II), were synthesized from the racemic phosphorus–chlorine compound (R,S)‐(Cl)P(O)(OC₆H₅)(NHC₆H₄‐p‐CH₃). Furthermore, the phosphorus–chlorine compound ClP(O)(OC₆H₅)(NH‐cyclo‐C₆H₁₁) was synthesized for the first time and used for the synthesis of rac‐phenyl (benzylamido)(cyclohexylamido)phosphinate, C₁₉H₂₅N₂O₂P, (III). The strategies for the synthesis of racemic mixed‐amide phosphinates are discussed. The P atom in each compound is in a distorted tetrahedral (N¹)P(=O)(O)(N²) environment. In (I) and (II), the p‐tolylamido substituent makes a longer P—N bond than those involving the N‐methylcyclohexylamido and allylamido substituents. In (III), the differences between the P—N bond lengths involving the cyclohexylamido and benzylamido substituents are not significant. In all three structures, the phosphoryl O atom takes part with the N—H unit in hydrogen‐bonding interactions, viz. an N—H...O=P hydrogen bond for (I) and (N—H)(N—H)...O=P hydrogen bonds for (II) and (III), building linear arrangements along [001] for (I) and along [010] for (III), and a ladder arrangement along [100] for (II).     

Hydrophosphinoyl derivatives of calix[4]resorcinarenes

Calix[4]resorcinarene reacts with N,N,N",N"-tetraethyl-P-ethylphosphonous diamide to give dioxaphosphocines, whose hydrolysis with intracavity water yields phosphinoyl derivative of calix[4]resorcinarene.     

HYDROLYSE DE SPIROPHOSPHORANES II. Derives de l'Octamethyl-2,2,3,3,7,7,8,8 Tetraoxa 1,4,6,9 Phospha V-5 Spiro 4,4 Nonane

Abstract

L'étude de l'hydrolyse de tetraoxaspirophosphoranes dérivés du pinacol et [sgrave] liaison P–C extracyclique a permis de mettre en évidence des équilibres esters cycliques–esters acycliques dépendant de différents facteurs (substituants, solvant, température, nature du milieu etc….). Les réactions d'hydrolyse peuvent ětre orientées sélectivement vers la formation soit de diesters soit de monoesters phosphoniques, cycliques ou acycliques.

Cyclic-acyclic esters equilibria have been found in the study of pinacol derivated tetraoxaspirophosphorans hydrolysis. These equilibria depend on different factors (substituents, solvent, temperature, basicity etc….). Hydrolysis reactions can be directed towards the formation of either diesters or cyclic and acyclic phosphonic monoesters.     

The use of POSS as synergist in intumescent recycled poly(ethylene terephthalate)

Fire retarded poly(ethylene terephthalate) (PET) has been obtained by the incorporation of octamethyl polyhedral oligomeric silsesquioxane (OMPOSS) and Exolit OP950, a phosphinate-based compound, in recycled PET. The presence of Exolit OP950 only leads to intumescence explaining the improvement of the flame retardancy. The addition of OMPOSS leads to a synergistic effect considerably increasing the fire retarding performances of the polymer in terms of cone calorimetry and limiting oxygen index even if a small thermal stabilisation as well as a very poor dispersion of OMPOSS and OP950 into the matrix has been observed.