58196-21-7

Upstream product

• 767-00-0 4-cyanophenol 

Downstream Products

• 107474-47-5 tris(O-4-cyanophenyl)phosphorothionate 
• 1241580-24-4 tris(O-4-cyanophenyl)phosphoroselenoate 
• 81592-05-4 hippuric acid-(4-cyano-phenyl ester) 

Relevant academic research and scientific papers

The synthesis of tris(perfluoroalkyl)phosphines

Tris(perfluoroalkyl)phosphines, of interest as turtable alternatives to the carbon monoxide ligand, can be synthesised by the nucleophile mediated reaction of perfluoroalkyltrimethylsilanes with triphenylphosphite; the method can be extended to diphosphines. The Royal Society of Chemistry 2005.

Electronic effects in mixed N-heterocyclic carbene/phosphite indenylidene ruthenium metathesis catalysts

Five new complexes [RuCl2(SIMes)(Ind)(O-pXC5H4)] bearing different para-substituted triphenylphosphites (X = H, OCH3, CF3, Cl, SF5 and CN) were synthesised and used to study the effect of t

Substituent effects on 31P NMR chemical shifts and 1J P-Se of triarylselenophosphates

The effect of electron-withdrawing (EW) and electron-releasing (ER) substituents on the 31P NMR chemical shifts and the structural parameters of a series of tris-(p-X-aryl)selenophosphates is reported in this article. Similarly to O-aryl phosphates and O-aryl thiophosphates, EW groups attached to aromatic rings induce a shielding effect on the 31P NMR signal. After a detailed experimental and theoretical analysis, we confirmed that the selenium atom is the main part responsible for the charge density transfer toward phosphorus through a back-bonding effect. The obtained 1JP-Se values for the complete series agree with this observation. Supplemental materials are available for this article. Go to the publisher's online edition of Phosphorus, Sulfur, and Silicon and the Related Elements to view the free supplemental file.

Substituent effects on the 31P NMR chemical shifts of arylphosphorothionates

Six tris(aryloxy)phosphorothionates substituted in the para position of the aromatic rings were synthesized and studied by 31P NMR, X-ray diffraction techniques and ab initio calculations at a RHF/6-31G** level of theory, in order to find the main structural factors associated with the δ31P in these compounds. As the electron-withdrawing (EW) ability of the substituents was increased, an 'abnormal' shielding effect on δ31P of the arylphosphorothionates was observed. The analyses of the geometrical properties obtained through both experimental and theoretical methods showed that a propeller-type conformation is preferred for the arylphosphorothionates, except in the case of the tris(O-4-methylphenyl) phosphorothionate, since one of the aromatic rings is not rotated in the same direction as the other two in the solid state. The main features associated with the δ31P NMR of compounds 1-6 were a decrease of the averaged O-P-O angle and mainly the shortening of the PS bond length, which is consistent with an increase of the thiophosphoryl bond order as δ31P values go upfield. On the other hand, comparison of the experimental and calculated bond lengths and bond angles involving α bonded atoms to phosphorus of the six compounds suggested that stereoelectronic interactions of the type nπO-σ*PS, nπO- σ*P-OAr and nπS-σ* P-OAr could be present in the arylphosphorothionates 1-6.

On the mechanism of the nickel-catalysed regioselective cyclodimerization of isoprene

A study of various Ni-ligand catalysed oligomerizations of isoprene has shown that with π-acidic P ligands the selectivity to cyclodimers amount to 97%. A new type of ligand is introduced, viz. fluoroalkyl phosphites having π-acceptor properties comparable to those of, e.g. PCl3. With tris(hexafluoroisopropyl) phosphite the main product is 1,4-dimethy1-4-vinylcyclohexene. A detailed explanation based on a two-step mechanism is given. As to the first step, for a series of ligands having similar steric properties the changes in product distribution as a function of the electronic ligand parameter are explained in terms of a gradual change in HOMO-LUMO interactions between Ni and the olefins, with strong π-acidic ligands promoting the head-to-head coupling of the isoprene molecules. The second step, involving reductive elimination of a cyclodimer from the metal, shows an increasing selectivity towards substituted cyclohexenes for the head-to-head and tail-to-tail intermediates with increasing π-acidity of the ligand. The qualitative orbital treatment presented as an explanation is also applicable to reactions found for other metallacyclopentanes.