Synthesis of New Heterocyclic Mono‐ and Bisorganophosphorus Acids and Their Derivatives with 1,2‐Phenylene Fragments

The interaction of esters of phosphorous acid containing POSiMe₃ and PH fragments with anhydrides of phthalic and 2‐sulfobenzoic acids is proposed as convenient methods for the synthesis of new heterocyclic mono‐ and bisorganophosphorus acids and their derivatives with 1,2‐phenylene fragments, carboxyl and sulfonyl groups. Also some properties of the obtained compounds are presented.     

Synthesis of new types of aminomethylenediphosphorus-containing acids and their derivatives

Convenient methods for synthesis of various aminomethylenediphosphorus-containing acids and their derivatives starting from available trimethylsilyl esters of hypophosphorous and phosphorous acids, ethoxymethyleneimine hydrochlorides, and N-substituted formamides have been proposed. Selected properties of the obtained compounds have been examined.

     

A New and Efficient Procedure for Synthesis of 1,5‐Benzodiazepine Derivatives in Solution and under Solvent‐Free Conditions

Borax/phosphorous oxychloride (BPO) efficiently catalyzes the preparation of 1,5‐benzodiazepine derivatives of o‐phenylenediamines and ketones in solvent‐free and solution conditions. The reaction proceeds efficiently under ambient conditions giving excellent yields of the products. This new protocol allows the recycling of catalyst with no loss in its potency.     

Phosphorylation of 3',4',5,7-Tetramethyldihydroquercetin

3',4',5,7-Tetramethyldihydroquercetin was phosphorylated with phosphorous acid derivatives, and similar results were obtained with phosphorochloridites and phosphoramidites. The PIII derivatives obtained were subjected to oxidation. The structures of the products were determined by NMR spectroscopy.     

Reaction of polychloronitrosoethanes with phosphorous acid derivatives

Conclusion The reaction of polychloronitrosoethanes with phosphorous acid derivatives results in the formation of the corresponding O-phosphorylated alkylchloroformimines.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 5, pp. 1086–1089, May, 1987.     

Sterically oriented synthesis and structure of new perphosphorylated resorcinarenes

Tetraarylresorcinarenes in a chair conformation of C_2h symmetry were synthesized by sterically oriented condensation of aromatic aldehydes with resorcinol and 2-methylresorcinol. By further phosphorylation of resorcinarenes with phosphorous amides perphosphorylated derivatives were obtained with rctt configuration of substituents at internuclear methylidene bridges. Structure of these compounds was proved using NMR spectroscopy and X-ray diffraction analysis.     

Direct amination of uracils and similar compounds

Conclusions A direct amination of uracils and similar compounds to aminopyrimidine derivatives was carried out using amides of phosphoric acid or phosphorous acid as animating agents.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 3, pp. 655–662, March, 1969.The authors wish to thank L. A. Nikitina for the spectral investigations.     

Reaction of phosphorus dicyanide and tricyanide with carbonyl compounds

Conclusions Phosphorus dicyanide and tricyanide react with carbonyl compounds to form the corresponding -cyano-substituted derivatives of phosphorous acid.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 8, pp. 1884–1885, August, 1982.     

Cationic Amphiphiles of Methylphosphonates and Cholesterol Phosphocholines and Their Homo Derivatives

A method of synthesis of (PO) and (PN)-choline cholesteryl methylphosphonates and their homo derivatives of the cationic type is developed. These compounds were obtained by the Arbuzov reaction between bromomethane and cyclic cholesteryl phosphorous esters and amidoesters and subsequent aminolysis of the intermediate bromoalkyl phosphonates. Alkylation of trimethylamine with cholesteryl ethanediyl and propanediyl phosphates gives cholesterol phosphocholines and their homo derivatives.     

Synthesis of bis‐ and tris‐organophosphorus substituted amines and amino acids with PCH2N Fragments

The aminomethylation of the derivatives of trivalent organophosphorus acids, containing PH and POSiMe₃ fragments with various bis‐ and tris(alkoxymethyl)amines and bis(alkoxymethyl)amino acids, is proposed as a convenient method for the synthesis of new bis‐ and trisphosphorylated amines and amino acids as well as their derivatives with four and five coordinated phosphorus. Also the three‐components systems of phosphorous acid, paraformaldehyde, and amines are thoroughly investigated via the treatment of reaction mixtures with bis(trimethylsilyl)amine. © 2010 Wiley Periodicals, Inc. Heteroatom Chem 21:430–440, 2010; View this article online at wileyonlinelibrary.com . DOI 10.1002/hc.20616     

Phosphorylation of β-cyclodextrin with substituted secondary hydroxy groups using phosphorous acid diamide

Phosphorylation of β-cyclodextin with substituted secondary hydroxy groups using 1,2-O,O′-isopropylideneglyceryl phosphorous diamide as a phosphorylating agent, in contrast to phosphorylation with trivalent phosphorus acid chlorides, is found to proceeds under mild conditions, but only in homogenous medium, and to afford acyclic diesteroamidophosphite derivatives of β-cyclodextin.     

Synthesis of new functionalized aryl‐substituted methylphosphonic and methylenediphosphonic acids and their derivatives

The convenient syntheses of new aryl‐substituted hydroxymethylphosphonic and methylenediphosphonic acids from the aromatic aldehydes, their derivatives, and phosphorous acid esters in the presence of the effective catalysts (trimethylsilyl trifluoromethanesulfonate, zinc chloride, and cadmium iodide) were developed.     

Pyridazine Derivatives and Related Compounds,Part 1. Some Reactions with 4-Cyano-5,6-Diphenyl-2,3-Dihydropyridazine-3-One

4-Cyano-5,6-diphenyl-2,3-dihydropyridazine-3-onc 1 reacts with phosphorous oxychloride to give 70% of the corresponding 3-chloro derivative 2. Treating 2 with anthranilic acid in butanol, 4-cyano-2,3-diphenyl-10H-pyridazino[6,1-b]quinoxaline-10-one, 3 was obtained. Compound 1 reacts with phosphorous pentasulphide to give 3-mercapto derivative 4, which was converted by acrylonitrile to S-(2-cyanoethyl)pyridazine derivative 5. Compound 4 reacts with ethyl bromoacetate and with phenacyl bromide gave the corresponding thieno[2,3-c] pyridazine derivatives 8, 9, Alkylation of 1 with ethyl chloroacetate afforded 3-0-carbethoxymethyl derivative 10. Compound 10 reacts with amines (aniline, hydrazine) to give the corresponding amide and acid hydrazide 13, 12 respectively. Hydrolysis of 10 with sodium hydroxide gave the corresponding acid derivative 11. Treating 1 with methyl iodide, 3-0-methyl derivative 14 was obtained, which was converted by ammonium acetate/acetic acid to 3-amino-4-cyano-5,6-diphenyl pyridazine 15. Compound 1 reacts with methyl magnesium iodide gave 4-acetyl derivative 16, which was reacted with hydrazine, phenyl hydrazine and with hydroxylamine to give the substituted I H pyrazolo [3,4-c] pyridazine 17 a,b and isoxazolo [5,4-c] pyridazine 18 derivatives respectively.     

Synthesis and properties of enamine derivatives of 1-methyl-2-phenyl-5-pyrrolone and 5-thiopyrrolone

The corresponding dimethylaminomethylene derivative, from which a number of similar compounds were synthesized by reaction with amines, was obtained by the reaction of 1-methyl-2-phenyl-2-hydroxy-5-oxotetrahydropyrrole with dimethylformamide in the presence of phosphorous oxychloride. The formyl derivatives of 1-methyl-2-phenyl-5-pyrrolone and 5-thiopyrrolone were obtained, and the UV and IR spectra of the enamines of these compounds were studied.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 6, pp. 791–793, June, 1972.     

Thermochemical characteristics of phosphorous acid derivatives

Enthalpies of formation enthalpies of a series of phosphorous acid derivatives were estimated from the heat effects of their reactions. The collected thermochemical data was used to analyze, on the basis of the additive scheme, the experimental enthalpies of formation and vaporization of four-coordinate phosphorus derivatives. Original Russian Text E.V. Sagdeev, Yu.G. Safina, 2007, published in Zhurnal Obshchei Khimii, 2007, Vol. 77, No. 2, pp. 275–279.     

Efficient One‐Pot Synthesis of Novel Spirooxindole‐Fused Phosphorous Heterocycle Derivatives by a Three‐Component Domino Reaction

A highly efficient, catalyst‐free, and regioselective synthesis of structurally diverse spirooxindole‐fused phosphorous heterocycle derivatives was constructed in good yields by means of a three‐component domino reaction of isatins, dichlorophenylphosphine or phenyl phosphorodichloridite, and o‐aminophenol in tetrahydrofuran reflux. The advantages of this method include high efficiency, mild reaction conditions, and environmentally benign reagents. These spirooxindole‐fused phosphorous heterocycles are promising candidates for drug discovery.     

Novel Vilsmeier-type methylenation for synthesis of dipyrazolylmethane derivatives using formamide or N-methylformamide

A novel Vilsmeier-type methylenation for synthesis of dipyrazolylmethanes was developed by reacting pyrazolones with formamide or N-methylformamide in the presence of phosphorous oxychloride POCl₃ coupling agent. This method can efficiently provide a series of dipyrazolylmethane derivatives as the main products in excellent yields without the formylated products. Our experimental result was different with the classical Vilsmeier-type reaction.     

Synthesis of thiadiazoles and 1,2,4-triazoles derived from cyclopropane dicarboxylic acid

New heterocyclic derivatives of cyclopropane dicarboxylic acid comprising thiadiazole and 1,2,4-triazole moieties are reported. Reaction of 1,1-cyclopropane dicarboxylic acid (1) with thiosemicarbazide and phosphorous oxychloride resulted in 1,1-bis (2-amino-1,3,4-thiadiazol-5- yl)cyclopropane (2). Cyclopropane dicarboxylic acid thiosemicarbazide (6) was converted into 1,1-bis(3-thio-4H-1,2,4-triazol-5-yl) cyclo- propane (7) by ring closure in an alkaline medium. The thiadiazole 2 and the triazole 7 were converted into a variety of derivatives.     

Halochromism of thiophene-containing analogs of chalcones and their derivatives

The formation of hydroxy-, acyloxy-, chloro-, and tetrachlorophosphoroxycarbonium ions was established on the basis of the electronic absorption spectra of thiophene-containing analogs of chalcones and their derivatives in concentrated sulfuric acid, in dilute solutions of sulfuric acid in acetic and trichloroacetic anhydrides, and in acetonitrile benzene, dichloroethane, and nitromethane in the presence of phosphorous pentachloride.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 10, pp. 1361–1364, October, 1971.     

First Representatives of Nitrophospholipids

General regularities of the phosphorylation of trimethylolnitromethane and its derivatives with amides and amidoesters of phosphorous acids were investigated. These procedures were found to hold promise for the design of amphiphilic phospholipids of a new type.__________Translated from Zhurnal Obshchei Khimii, Vol. 75, No. 7, 2005, pp. 1100–1105.Original Russian Text Copyright © 2005 by Predvoditelev, Malenkovskaya, Sipin, Nifant’ev.