I. F. Lutsenko

ALKYLATION AND ACYLATION OF TETRAALKOXYDIPHOSPHINES

Die Methylierung des Tetrabutoxydiphosphins (I) mit Methyljodid (II) ergibt unter Umlagerung die Verbindung (III), die mit Wasser zu Dimethylphosphinsaure (V) und Dibutylphosphit (IV) hydrolysiert wird.

Investigation of functionally substituted organic derivatives of phosphorus acids by the method of high-resolution PMR

1. n nThe products of the reactions ofα-metallized aldehydes, ketones, and esters of carboxylic acids with halides, hydrides, and sulfides of groups IV and V of the Periodic System were studied by the PMR method. Their C- (types 1 and 3) and O- (type 2) structure was established: n n n n n n n2. n nThe inductive influence of substituents directly bonded to the phosphorus atom was studied. The change in the parameters of the PMR spectra of acetonyl derivatives of tri- and pentavalent phosphorus is of the same type. The differences in the valence state of the phosphorus atom, as well as the replacement of oxygen by sulfur, have no effect upon the parameters of the PMR spectra. Substituents are arranged in the following order with respect to influence on the chemical shift of the methylene protons: Cl > C6H5 > OAlk > Alk. n n n n n3. n nA comparison of the PMR data on the derivatives of tri- and pentavalent phosphorus containing the isopropenyloxy group gives a series of influence of substituents differing from that cited above: Cl > OAlk > C6H5 > Alk. n n n n n4. n nFor derivatives of phosphonous and phosphinous acids, containing a carbalkoxymethyl group at the phosphorus atom, the change in the chemical shifts of the protons of the methylene group is correlated with the change in the inductive effect of the substituent at the phosphorus atom, while no obvious patterns are observed in the change of the spin-spin interaction constants JP-C-H.