Reactions of Bis(chloromethyl)phosphinic(-Phosphinothioic) Chlorides with Silylated Carbamates and Trimethylsilyl N-Trimethylsilylacetimidoate

Bis(chloromethyl)phosphinic chloride reacts with trimethylsilyl methylcarbamate in benzene in the presence of a base to give trimethylsilyl bis(chloromethyl)phosphinate. The same reaction performed without a solvent and in the absence of a base yields trimethylsilyl bis(chloromethyl)phosphinate and bis(chloromethyl)phosphinic anhydride. Reaction of bis(chloromethyl)phosphinic chloride with trimethylsilyl diethylcarbamate yields N,N-diethylbis(chloromethyl)phosphinic amide. The reaction of bis(chloromethyl)phosphinic (-phosphinothioic) chlorides with trimethylsilyl N-trimethylsilylacetimidoate was studied.     

Synthesis of some derivatives of bis (N,N-dialkylaminomethyl)phosphinic acids

Conclusions A number of derivatives of bis(N,N-dialkylaminomethyl)phosphinic acids have been obtained by the reaction of dialkylamines with esters and amides of bis(chloromethyl) phosphinic acid.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 6, pp. 1346–1348, June, 1967.     

Synthesis of alkyl- and aryl(o-oxyphenoxymethyl) phosphinic acids

Conclusions Cleavage of 2-oxo-2-chloromethyl-1,3,2-benzodioxaphosphole by Grignard reagents produced pyrocatechol esters of alkyl- and aryl(chloromethyl)phosphinic acids, cyclization of which and subsequent hydrolysis lead to alkyl- and aryl(o-oxyphenoxymethyl)phosphinic acids.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 4, pp. 943–946, April, 1989.     

Kinetics of the alkaline hydrolysis of bis(chloromethyl)phosphinic esters

Conclusions The kinetics of the hydrolysis of bis (chloromethyl)phosphinic esters was investigated in KOH medium at 10 and 25°. The rate constants are correlated with the steric constants of the leaving groups.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 4, pp. 923–924, April, 1967.     

Kinetics of the hydrolysis of ethers of bis(chloromethyl)phosphinic acid

Conclusions A study was made of the hydrolysis kinetics of some esters of bis(chloromethyl)phosphinic acid in water at 75–95°. The reaction rate depends on the nature of the alcohol radical, and for the alkyl radicals is determined by the steric factor.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 9, pp. 1654–1655, September, 1966.     

Structures of Metal Complexes with Anions of Di(hydroxymethyl)phosphinic and Di(chloromethyl)phosphinic Acids

This paper considers the structural features of complexes containing Ag(I), 3dmetals (Cu and Ni), and rare-earth elements (REE) such as La, Nd, Er, and Lu, alkaline-earth (Sr) or alkaline (Li, Na) metals with anions of di(hydroxymethyl)phosphinic (L¹) or di(chloromethyl)phosphinic (L²) acids with a general formula RR"PO^– ₂, where R = R" = OH and Cl for L¹and L², respectively. Different patterns of coordination between organophosphorus acids and different metals (four for each L¹and L²) are described. Structures of copper(II) complexes with L¹and L²were compared with those of Cu(II) with dialkyl- and diaryl-substituted monophosphonic and aminophosphinic acids.     

Acid-base properties of bis(chloromethyl)phosphinic acid para-nitroanilide in aqueous micellar solutions of surface active agents

Micelles of the cation-active surface active agent (SAA), cetyltrimethylammonium bromide, decrease the pK_a of bis(chloromethyl)phosphinic acid pnitroanilide in aqueous solutions by two units, while micelles of the anionactive SAA, sodium dodecyl sulfate increase the pK_a of the same compound by 1.75 units. The presence of electrolytes in the solution lowers the influence of micelles on the acid-base properties of the anilide.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 5, pp. 991–994, May, 1990.     

Organic phosphorus compounds : LXXI. Preparation,properties, and structure of bis(aminomethyl)phosphinic acid, (H2NCH2)2P(O)OH

Bis(aminomethyl)phosphinic acid, (H₂NCH₂)₂P(O)OH · HCl, was prepared by debenzylation of (C₆H₅CH₂NHCH₂)₂P(O)OH · HCl with hydrogen using 5% Pd on C as catalyst, and from bis(t-butylaminomethyl)phosphinic acid, (t-C₄H₉NHCH₂)₂P(O)OH, by isobutylene elimination in concentrated aqueous hydrobromic acid at 175°C in sealed tube. Interaction of bis(chloromethyl)phosphinic acid with ammonia in an autoclave produced methylaminomethylphosphinic acid, CH₃NHCH₂P(O)(OH)₂. A mechanism for the formation of this product is proposed. Several derivatives of (H₂NCH₂)P(O)OH such as (RNHCH₂)₂P(O)OH, R = C₆H₅CO, CICH₂CO, [H₂NHNC(=NH)NHCH₂]₂P(O)OH and [(CH₃)₃SiNHCH₂]₂P(O)OSi(CH₃)₃ were prepared.     

New organized systems based on amphiphilic oxyethylated calix[4]arene

The aggregation of amphiphilic oxyethylated calix[4]arene is studied in the absence and presence of polyethyleneimine. At low calixarene concentrations, large ensembles with a hydrodynamic diameter of about 100 nm are formed and coexist with small (smaller than 10 nm) aggregates, which are observed in the entire concentration range. It is established that calixarene-based systems catalyze the neutral hydrolysis of bis(chloromethyl)phosphinic acid p-nitrophenyl ester, with the catalytic effect being as high as two orders of magnitude in the presence of La(III) ions. The rate of hydrolysis of phosphonates depends on the composition of the supramolecular system. The maximum acceleration exceeds three orders of magnitude in comparison with alkaline hydrolysis of the substrates.     

Dissociation constants of organophosphinic acid compounds

The dissociation equilibria of di(2,4,4-trimethylpentyi) phosphinic acid, mono(2,4,4-trimethylpentyl) phosphinic acid, di(n-octyl)phosphinic acid and mono(n-octyl)phosphinic acid have been studied in ethanol-water mixtures by potentiometric titration at 25 degrees C. These data have been analysed both graphically numerically using the program LETAGROP-ZETA. The obtained pK(a) values have been correlated with the corresponding values in water, determined both indirectly by means of extraction measurements and by estimation using the suitable Hammett equation.     

Synthesis of P,N-heterocycles from omega-amino-H-phosphinates: conformationally restricted alpha-amino acid analogs

P,N-heterocycles (3-hydroxy-1,3-azaphospholane and 3-hydroxy-1,3-azaphosphorinane-3-oxide) are synthesized in moderate yield from readily available omega-amino-H-phosphinates and aldehydes or ketones via an intramolecular Kabachnik-Fields reaction. The products are conformationally restricted phosphinic analogs of alpha-amino acids. The multigram-scale syntheses of the H2N(CH2)(n)PO2H2 phosphinic precursors (n = 1, 2, 3) and some derivatives are also described.     

Synthesis of bis(chloromethyl) derivatives of diphenyl sulfide,thianthrene, and dibenzothiophene

Conclusions The chloromethylation of diphenyl sulfide, thianthrene, and dibenzothiophene, respectively, gave 4,4-bis(chloromethyl)diphenyl sulfide, 2,6-bis(chloromethyl)thianthrene, and 2,7-bis(chloromethyl)dibenzothiophene.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 12, pp. 2799–2801, December, 1976.     

Synthesis,Crystal Structure and Complexing Properties of Phosphinic Analogues of Glycylglycine

Abstract

The phosphinic dipeptides of the general formula H₂NCH₂CONHCH₂P(R)(O)(OH) where R?Me, Ph and t-Bu has been synthetized from the free phosphinic acids and N-hydroxnunimide esters of the N-protected glycine. The deprotected dipeptida were purified by combination of the column chromato graphy on strong and week cation exchange resins by elution with diluted aqueous ammonia (0.1–3%)     

A novel method for the separation of bis(alpha-hydroxyalkyl)phosphinic acid diastereoisomers via formation of novel cyclic phosphinic acids

The reaction of aromatic and aliphatic aldehydes with hypophosphorus acid under microwave irradiation was examined. The reaction gave a mixture of a racemic pair of bis(alpha-hydroxyalkyl)phosphinic acids and acetal derivatives from the corresponding bis(alpha-hydroxyalkyl)phosphinic acids of meso-stereochemistry in good yield. The difference in solubility in organic solvents due to polarity allowed us to readily separate these compounds. This method constitutes an easy, rapid, and good-yielding preparation and separation of bis(alpha-hydroxyalkyl) phosphinic acid diastereoisomers from simple starting materials using microwave irradiation.     

Active methylene phosphinic peptides: a new diversification approach

[reaction: see text] Simple, rapid, and efficient methods for P(1)' diversification of phosphinic peptides have been developed, employing alkylation and Knoevenagel-type condensation reactions with active methylene phosphinic scaffolds, thus leading to a wide variety of diversified phosphinic and dehydrophosphinic peptides.     

Protection of the Hydroxyphosphinyl Function of Phosphinic Dipeptides by Adamantyl. Application to the Solid-Phase Synthesis of Phosphinic Peptides

To develop solid-phase synthesis of phosphinic peptides, different FmocXaaPsi{PO(OAd)CH(2)}XaaOH building blocks have been prepared, where Fmoc is (fluorenylmethoxy)carbonyl. In this respect, the protection of the hydroxyphosphinyl function in these phosphinic dipeptides by the adamantyl group turns out to be convenient. The phosphinic adamantyl esters are completely stable in basic conditions and can be removed under relatively mild acidic conditions. Using these building blocks, despite the bulkiness of the adamantyl group, no particular problem of coupling was observed during the solid-phase synthesis of phosphinic peptides by the Fmoc strategy. The developed methodology is of particular interest to facilitate the development of potent inhibitors of zinc-metalloproteases.     

Physicochemical characterization of phosphinic pseudopeptides by capillary zone electrophoresis in highly acidic background electrolytes

Phosphinic pseudopeptides (i.e., peptide isosteres with one peptide bond replaced by a phosphinic acid moiety) were analyzed and physicochemically characterized by capillary zone electrophoresis in the pH range of 1.1-3.2, employing phosphoric, phosphinic, oxalic and dichloroacetic acids as background electrolyte (BGE) constituents. The acid dissociation constant (pK(a)) of phosphinate group in phosphinic pseudopeptides and ionic mobilities of these analytes were determined from the pH dependence of their effective electrophoretic mobilities corrected to standard temperature and constant ionic strength of the BGEs. It was shown that these corrections are necessary whenever precise mobility data at very low pH are to be determined. Additionally, it was found that the ionic mobilities of the phosphinic pseudopeptides and pK(a) of their phosphinate group are affected by the BGE constituent used. The variability of migration behavior of the pseudopeptides can be attributed to their ion-pairing formation with the BGE components.     

A novel synthesis of bis-(α-hydroxyalkyl)phosphinic acids involving microwave irradiation

A simple, efficient, and general method has been developed for the synthesis of bis-(α-hydroxyalkyl)phosphinic acids from hypophosphorous acid using microwave irradiation. Bis-(α-hydroxyalkyl)phosphinic acids were obtained in high yield under mild conditions by reaction of hypophosphorous acid with aldehydes under microwave irradiation.     

Organosilicon derivatives of 2-mercapto-substituted benzoxazoles,benzothiazoles and benzimidazoles

The interactions of sodium salts of 2-mercaptobenzoxazole, 2-mercaptobenzothiazole and 2-mercaptobenzimidazole with (chloromethyl)trimethyl-, chloromethyl(dimethoxy)methylor (chloromethyl)trimethoxysilanes have been shown to result in the corresponding previously unknown (2-heterylthiomethyl)triorganylsilanes. Transetherification of (2-heteryl-thiomethyl)trimethoxysilanes with triethanolamine gives 1-(2-benzoxazolylthiomethyl)-, 1-(2-benzothiazolylthiomethyl)- and 1-(2-benzimidazolylthiomethyl)silatranes. The reaction of the corresponding alkoxysilanes with boron trifluoride etherate leads to (2-benzoxazolylthiomethyl)- and (2-benzothiazolylthiomethyl)-substituted trifluorosilanes and methyldifluorosilanes having a dragonoid chelate structure. By the hydrolysis of (2-heterylthiomethyl)trimethoxysilanes, new organosilicon sorbents, poly(2-heteryl-thiomethyl)silsesquioxanes have been synthesized.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 11, pp. 1965–1969, November, 1993.