The reaction of glyoxylic acid monohydrate with mesityl(phenyl)phosphine in air led to the formation of mesityl(phenyl)phosphine oxide glycolate. The synthesized mesityl(phenyl)phosphine oxide glycolate has been characterized by various analytical methods including X-ray crystal structure analysis. The analysis of intermolecular interactions in the crystal revealed interesting modes of the noncovalent bonding between pairs of molecules. These intermolecular interactions cause the formation of one-dimensional cylindrical channels with diameter of 1 nm (10 angstrom) and provide the crystal with the properties of precise nano-sized crystalline porous material which can be served as the component for precise nanofiltration membranes improving the properties of amorphous polymers which suffer from disordered pore structures and reduced selectivity towards separating molecules.
It has been experimentally shown that N-heteroaryl-substituted α-diphenylphosphinoglycines N-(pyrazin-2-yl)-α-diphenylphosphinoglycine, N-(pyridin-2-yl)-α-diphenylphosphinoglycine and N-(pyrimidin-2-yl)-α-diphenylphosphinoglycine obtained by the reaction of three-component condensation of diphenylphosphine, the corresponding primary amine and glyoxylic acid monohydrate are capable in combination with Ni(COD)₂, where COD is cyclooctadiene-1,5, to form active forms of catalysts for selective homogeneous dimerization and trimerization of ethylene with the formation of butene-1 and hexene-1 as the main products. It has been established that the obtained organo-nickel catalytic systems provide a yield of short-chain (C₄–C₆) olefins at the level of 90% with a selectivity for linear α-olefins of 97%. The study of the influence of temperature on the process of homogeneous ethylene oligomerization using the obtained compounds made it possible to establish that the optimal temperature for ethylene oligomerization, providing the highest selectivity to butene-1 and hexene-1, is 80–105°C at the optimum pressure of ethylene is 20–35 atm. Under these conditions, the selectivity for butenes is 71.4–72.6% (selectivity for butene-1 – 69.3–71.1%), for hexenes 20.6–21.2% (selectivity for hexene-1 – 19.2–19.5%), and the optimal duration of the oligomerization process at a temperature 105°C is 1.5 h, which provides the rate of formation of butene-1 equal to 168.1 golig gNi⁻¹h⁻¹) and the rate of formation of hexene-1 – 47.3 golig gNi⁻¹h⁻¹).
Quantum-chemical calculations were performed to rationalize the experimental molecular weight distribution of α-olefin products, revealing the main mechanistic models of the process.
The electrochemical properties of the N-substituted α-diphenylphosphinoglycines N-(2-methoxybenzyl) diphenylphosphinoglycine (1), N-(pyrazin-2-yl) diphenylphosphinoglycine (2), N-(1-adamantyl) diphenylphosphinoglycine (3), and N-(2,5-dimethoxycarbonylphenyl) diphenylphosphinoglycine (4) obtained in the three-component condensation of diphenylphosphine, glyoxylic acid hydrate, and the corresponding amine were studied by cyclic voltammetry on a glassy carbon electrode. The structure of compound 4 was confirmed by X-ray diffraction analysis. Compounds 1–4 exhibited electrochemical activity in the anodic region of potentials due to the presence of an oxidizable diphenylphosphine fragment in the molecule. Compound 4 can also be electrochemically reduced at the cathodic potentials of the working electrode due to the ester groups in the aromatic fragment.
The relative thermodynamic stability of unionized and zwitterionic forms of α-phosphino-α-amino acids is governed by the substituent R at the nitrogen atom, namely, (het)aryl substituents favour the formation of the unionized form RHNCH(PPh2)COOH, while in the case of alkyl analogues the zwitterions RH2N+CH(PPh2)COO− predominate. The experimentally observed trends have been supported by quantum-chemical calculations. The synthesis and X-ray crystal structure analysis of a new unionized α-phosphino-α-amino acid [α-diphenylphosphino-N-(2-methoxycarbonylphenyl) glycine] are reported.
α-Diphenylphosphino-N-(pyrazin-2-yl)glycine was synthesized by the three-component condensation of diphenylphosphine, glyoxylic acid hydrate, and 2-aminopyrazine and its structure was confirmed by X-ray diffraction. It reacted with [Ni(COD)2] (COD is cycloocta-1,5-diene) to give complexes that were tested as catalysts for selective dimerization/oligomerization of ethylene to but-1-ene (main product) and C6–C14 α-olefins, respectively.