Phosphite ester

Abstract: Lubricating and functional fluid compositions which comprise at least one oil of lubricating viscosity and an extreme-pressure and friction-modifying amount of (A) at least one phosphite ester characterized by Formula (I), wherein R1 is a straight-chain hydrocarbyl group and R2 is a branched-chain hydrocarbyl group. The invention also relates to compositions which comprise the combination of such phosphite esters as represented by Formula (I) and various sulfur-containing compositions. The compositions comprising said combinations also are useful in lubricating and functional fluid compositions including lubricating oils and greases. Aqueous systems containing the phosphite esters represented by Formula (I) as well as combinations of phosphite esters with sulfur-containing compositions also are described.

Abstract: Methods are provided for preparing nucleic acid arrays on a support, particularly substantially planar supports. In one group of these methods a plurality of nucleic acids are synthesized on the support and the synthesis steps include oxidizing a phosphite triester nucleic acid linkage to a phosphate triester nucleic acid linkage using a solution about 0.005 M to about 0.05 M iodine in a mixture comprising water and organic solvent. In another group of these methods a plurality of nucleic acids are synthesized on the support and the synthesis steps include oxidizing a phosphite triester nucleic acid linkage to a phosphate triester nucleic acid linkage using a solution comprising iodine and at least 4% by volume of water.

Abstract: The calixarene phosphites L1–L4 were obtained in high yield through reaction of PCl3/NEt3 with the monofunctionalised cone-calixarenes p-tert-butylcalix[4]arene(OH)3OR, in which the R substituents bear an oxygen donor ligand [R = CH2P(O)Ph2 (L1), CH2CO2Et (L2), CH2C(O)NEt2 (L3), CH2CH2OMe (L4)]. The calixarene core of the four ligands adopts a cone conformation and, hence, the phosphites become potential P,O-chelating systems. Phosphite L1 is remarkably stable towards aqueous NaOH, but the presence of slightly acidic water results in phosphonate formation. Slow oxidation of L1 in air afforded the corresponding mixed phosphine oxide–phosphate. In the complexes [RuCl2(p-cymene)L1], [cis-PtCl2(L1)2] (9), trans-[PdCl2(L1)2], [Pd(8-mq)Cl(Ln)] (8-mqH = 8-methylquinoline, n = 1–3), [Pd(dmba)Cl(L1)] (dmbaH = N,N-dimethylbenzylamine), [Pd(η3-C4H7)Cl(L2)], [Rh(acac)(CO)Ln] (n = 1–3) and [RhCl(CO)(L1)2], the phosphites behave as a monodentate phosphorus donor ligands. Owing to their steric crowding, the two cis-disposed ligands of complex 9 cannot freely rotate about their coordination axis. In the solid state, the calixarene backbones of complex 9 display a so-called ‘up-up-out-up’ conformation. Chelating phosphite behaviour was found in the cationic complexes [Pd(8-mq)Ln]BF4 (n = 1–3). In solution, the large, chelating P,O-loop of the latter complexes swings from one side of the metal plane to the other, the dynamics possibly being facilitated by the flexibility of the calixarene backbone. The four oxo-functionalised phosphites were tested as catalysts for 1-octene hydroformylation. The observed reaction rates lie in the range reported for other medium-bulky phosphites. Furthermore, the hydroformylation rate decreases as the donor strength of the side group increases, suggesting binding of the O-donor during catalysis. The L/B ratios lie in the range 1.4–3.6, the highest linear aldehyde selectivity being observed with the phosphite ester L3.