Some properties of 1-phosphorus(IV)-substituted cycloalkanecarboxylic acids and their derivatives

An x-ray structural study of single crystals of 1-diphenylphosphinyl-cyclo-propane- and 1-diphenylphosphinylcyclobutanecarboxylic acids was conducted. 1-Phosphorylated cycloalkanecarboxylic acid amides were obtained from the corresponding acids by the reaction with thionyl chloride with subsequent treatment with primary and secondary amines. It was shown that the reaction of 1-phosphorylated 1-functional substituted cycloalkanes with trimethylbromosilane takes place with preservation of the cyclic structure and yields phosphoric acid silyl esters, and the corresponding cycloalkylphosphonic and cycloalkylphosphinic acids were synthesized by their hydrolysis in soft conditions.A. N. Nesmeyanov Institute of Organoelemental Compounds, Russian Academy of Sciences, 117813 Moscow. Translated from Izvestiya Akademii Nauk, Seriya Khimicheskaya, No. 8, pp. 1879–1888, August, 1992.     

Cycloalkylation of compounds in the series of phosphorus-substituted derivatives of acetic acid

1-Phosphoryl-substituted cyclopropanes, cyclobutanes, and cyclopentanes were obtained by the reaction of phosphoryl-substituted esters and nitriles of acetic acid with ,-dihaloalkanes. The influence of the CH-acidity of the starting compounds and electrophilicity of the alkylating agent on the reaction rate was examined.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 8, pp. 1873–1880, August, 1990.     

Reactions of phosphoryl- and thiophosphorylacetonitriles with poly(bromomethyl)arenes containing closely-spaced bromomethyl groups. New types of phosphorus-substituted fused systems

Reactions of phosphoryl- and thiophosphorylacetonitriles with poly((bromomethyl)arenes containing closely-spaced bromomethyl groups under conditions of phase-transfer catalysis occur as cycloalkylation to form new types of fused systems, in which aromatic rings are annelated with a five-, six-, or seven-membered ring containing the exocyclic phosphorus containing and cyano substituents. The reaction pathway is independent of the reagent ratio. Under the same conditions, the reaction with 1,3,5-tris(bromomethyl)-2,4,6-trimethylbenzene affords products of monoalkylation at all electrophilic groups of the starting substrate. In the resulting compounds, the alkoxy groups at the phosphorus atom are easily transformed into the hydroxy groups via the corresponding silyl ethers to give the corresponding phosphorus acids, whereas the cyano group is chemically inert.__________Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 3, pp. 745-756, March, 2005.     

Effect of phosphoryl and thiophosphoryl groups on CH acidities

It is shown that the CH acidities of phosphoryl and thiophosphoryl compounds depend on the substituents attached to both the carbon atom and the phosphorus atom and comply with Hammett dependences; the parameters of the correlation dependences are very close for the two types of compounds, and this makes it possible to propose a general equation for calculating the pK values of CH acids that contain a phosphoryl or thiophosphoryl group.A. N. Nesmeyanov Institute of Heteroorganic Compounds, Academy of Sciences of the USSR, Moscow. Translated from Teoreticheskaya i Éksperimental'naya Khimiya, Vol. 27, No. 3, pp. 284–288, May–June, 1991. Original article submitted February 18, 1991.     

Synthesis and complexing properties of phosphoryl-substituted salicylaldimines

Starting from meta and ortho isomers of (diphenylphosphorylmethyl)anilines 2a,b, procedures were developed for the synthesis of new phosphoryl-substituted Schiff bases 3a,b serving as tridentate ligands. In alcoholic solutions, ligands 3a,b form complexes of different composition with praseodymium and neodymium nitrates. Only the M(L)₂(NO₃)₃ complexes crystallized from solution regardless of the reactant ratio. According to the X-ray diffraction study and IR spectroscopy, one of the ligands in the complexes with ortho ligand 3b is coordinated in a bidentate fashion via the oxygen atom of the P=O group and the phenoxy oxygen atom, whereas the second ligand molecule forms a coordination bond with metal only via the phosphoryl oxygen atom. In the Pr(3a)₂(NO₃)₃ complexes, both meta ligands 3a are involved in thebidentate O,O-coordination. Dedicated to Academician G. A. Abakumov on the occasion of his 70th birthday. Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 9, pp. 1827–1835, September, 2007.     

Interaction of 2-methyl-2,5-dioxo-1,2-oxaphospholane with trimethylsilyl cyanide

The reaction of 2-methyl-2,5-dioxo-1,2-oxaphospholane (1) with trimethylsilyl cyanide was found to give, depending on conditions, three organophosphorus compounds: trimethylsilyl methyl(2-cyanocarbonylethyl)phosphinate (2), trimethylsilyl methyl(3-trimethylsiloxy-3,3-dicyanopropyl)phosphinate (3) and trimethylsilyl methyl(3-trimethyl-siloxy-3-cyano-2-propenyl)phosphinate (4), On hydrolysis of3 under mild conditions, methyl(3-hydroxy-3,3 dicarboxypropyl)phosphinic acid (7) was obtained. The latter is readily decarboxylated on heating to give methyl(3-hydroxy-3-carboxy-propyl)phosphinic acid (8). The interaction of2 and4 with water or alcohols gives, correspondingly, methyl[2-carboxy(alkoxycarbonyl) ethyl]phosphinic acids (11–13). Methyl(2-oxamoyiethyl)phosphinic acid (14) was prepared by successive treatment of propenylphosphinate4 with HCl gas and water.Translated fromIzvestiya Akademii Nauk, Seriya Khimicheskaya, No. 1, pp. 170–177, January, 1993.